JP5098332B2 - Polymerization catalyst composition containing metallocene complex and polymer produced using the same - Google Patents

Abstract

The present invention provides a novel catalyst composition comprising a metallocene complex, and a novel producing method for various polymer compounds. Preferably, the invention provides a novel polymer compound, and a producing method thereof. Specifically, the invention provides a polymerization catalyst composition, comprising: (1) a metallocene complex represented by the general formula (I), including: a central metal M which is a group III metal atom or a lanthanoid metal atom; a ligand Cp* bound to the central metal and including a substituted or unsubstituted cyclopentadienyl derivative; monoanionic ligands Q 1 and Q 2 ; and w neutral Lewis base L; and (2) an ionic compound composed of a non-ligand anion and a cation: where w represents an integer of 0 to 3.

Description

The present invention relates to a polymerization catalyst composition containing a metallocene complex, and more particularly to a polymerization catalyst composition in which the central metal of the metallocene complex is a Group 3 metal or a lanthanoid metal.
The present invention also relates to a method for producing a polymer compound characterized by using the polymerization catalyst.
Furthermore, the present invention relates to a polymer compound, particularly a high syndiotactic polymer of styrene, and a styrene-ethylene high syndiotactic copolymer, which can be produced using the polymerization catalyst composition.

  A metallocene complex is a compound that is used as one of catalyst components for various polymerization reactions, and is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal. Among these, a metallocene complex having one cyclopentadienyl or a derivative thereof bonded to a central metal may be referred to as a half metallocene complex.

  Metallocene complexes have completely different characteristics (including catalytic activity for polymerization reaction) depending on the type of central metal. As for metallocene complexes in which the central metal is a Group 3 metal or a lanthanoid metal atom, for example, the following reports have been made.

  1. It is disclosed that a complex represented by the structural formula (II) can be used as a component of a polymerization catalyst system (see Patent Document 1). The complex disclosed in this document is characterized by containing a bridged ligand having cyclopentadienyl (or a derivative thereof).

2. A hydride complex represented by (C ₅ Me ₄ SiMe ₃ ) LnH ₂ (THF) (Ln represents a Group 3 metal or a lanthanoid metal; the same applies hereinafter) is known (for example, Non-Patent Document 1). reference). A complex represented by (C ₅ Me ₄ SiMe ₃ ) Ln (CH ₂ SiMe ₃ ) ₂ (THF) used as a precursor of the hydride complex is also known.
Of (C ₅ Me ₄ SiMe ₃ ) LnH ₂ (THF), [(C ₅ Me ₄ SiMe ₃ ) YH ₂ ] ₄ (THF) (tetranuclear complex) reacts with styrene to give a 1: 1 addition. It is reported that it gives a body and does not show polymerization activity (see Non-Patent Document 6, for example).
3. Of the above-mentioned (C ₅ Me ₄ SiMe ₃ ) Ln (CH ₂ SiMe ₃ ) ₂ (THF), it is known that a complex in which Ln is yttrium Y does not exhibit a polymerization activity for styrene (Non-Patent Document). 2).
4). Also known is the complex (C ₅ Me ₄ SiMe ₃ ) La (CH ₂ (SiMe ₃ ) ₂ ) ₂ (THF), which is combined with methylaminoxan (MAO) or alone, It can be used as a catalyst for polystyrene polymerization and has been reported to give atactic polystyrene (see Non-Patent Document 3).

  However, the usefulness of metallocene complexes (particularly metallocene complexes in which the central metal is a Group 3 metal or a lanthanoid metal) as a polymerization catalyst component has not yet been fully elucidated, and further research has been desired.

On the other hand, the styrene polymer is a syndiotactic styrene polymer obtained by a polymerization reaction using a metallocene complex in addition to an atactic styrene polymer called general grade polystyrene (GPPS) or impact-resistant polystyrene (HIPS). Coalescence (sPS) is produced industrially. The synthesis of sPS was announced by Idemitsu Kosan in 1986, and was synthesized using a catalyst system containing a titanium metallocene complex (see, for example, Non-Patent Document 4). Examples of the catalyst system include CpTiX ₃ / MAO, CpTiR ₃ / B (C ₆ F ₅ ) ₃ (Cp is substituted or unsubstituted cyclopentadienyl or indenyl: X is halide or alkoxy: R is alkyl: MAO is methylaluminoxane) or the like.
Although sPS synthesized in this way has high syndiotacticity, it has a feature that the molecular weight distribution is slightly broad (see, for example, Patent Documents 2 to 3), and sPS having a narrower molecular weight distribution is of interest. It was a compound possessed.

  sPS is a polymer that has a high melting point (about 270 ° C.), good crystallinity, excellent heat resistance, chemical resistance, dimensional stability, and the like, and is widely used industrially. . However, on the other hand, it is pointed out that the molding process is difficult.

On the other hand, several reports have been made on the synthesis of ethylene-styrene copolymers (see Non-Patent Document 5). The ethylene-styrene copolymers reported by these were copolymers that have no regioselectivity or stereoregularity with respect to the chain of styrene structural units. Accordingly, an ethylene-styrene copolymer having regioselectivity and a copolymer having high stereoregularity (particularly syndiotacticity) with respect to the styrene structural unit has been an interesting compound.
Furthermore, a method of synthesizing an isoprene-styrene copolymer having a high syndiotacticity of a styrene unit using a catalyst system of CpTiCl ₃ / MAO (Cp is cyclopentadienyl) has been reported (Non-patent Document 10). reference). The catalytic activity in this polymerization reaction is not sufficient, and further improvement is required. Furthermore, there are many unclear points regarding the physical properties of the synthesized isoprene-styrene copolymer.

  The cyclic olefin polymer is expected to be superior in heat resistance, strength, and elastic modulus because the movement of the polymer chain is restricted as compared with the non-cyclic olefin polymer. Furthermore, the potential as an optical material is expanding. However, cyclic olefin compounds generally have low polymerization activity due to their bulky molecules, and effective polymerization catalyst systems are limited.

  On the other hand, a 1,3-cyclohexadiene polymer obtained by polymerizing 1,3-cyclohexadiene, which is one of cyclic olefins, using a specific nickel catalyst has been reported (Non-patent Document 7). ). The polymer is characterized by a 1,4-selective addition polymerization of 1,3-cyclohexadiene and has been suggested to be cis-syndiotactic. There are no specific reports on the cityity or molecular weight.

  In addition, there are limited reports on copolymers of 1,3-cyclohexadiene, and copolymers of 1,3-cyclohexadiene and other olefins are interesting compounds. As a few examples, a copolymer of 1,3-cyclohexadiene and styrene obtained by anionic copolymerization using alkyllithium has been reported, but the copolymer has no regioregularity and stereoregularity. Nor.

  On the other hand, as for polymers of norbornenes which are one of cyclic olefins, ring-opening metathesis polymers and copolymers with ethylene are known. In particular, since a copolymer with ethylene is excellent in transparency and heat resistance, development to an optical material is expected (see Non-Patent Document 8). The present inventors found that norbornenes and copolymers containing ethylene and an aromatic component (ternary copolymers) have physical properties (for example, UV blocking properties) superior to those of norbornenes and ethylene copolymers. The production of the ternary copolymer was studied.

  Furthermore, dicyclopentadiene, which is one of norbornenes, has a C═C double bond derived from a norbornene structure and a C═C double bond derived from cyclopentene. Similar to norbornene, a copolymer with ethylene is an interesting compound, but recently it has been reported that it can be synthesized using a specific Zr complex as a polymerization catalyst (Non-patent Document 9). However, the copolymer of dicyclopentadiene and ethylene synthesized by the reported method has a limited molecular weight and dicyclopentadiene content.

International Publication No. WO 00/18808 Pamphlet JP 62-104818 JP-A-62-187708 Z. Hou et al., Organometallics, 22, 1171 (2004) J. Okuda et al., Angew. Chem. Int. Ed., 38, 227 (1999) K. Tanaka, M. Furo, E. Ihara, H. Yasuda, J. Polym. Sci. A: Polym. Chem. 39, 1382 (2001) N, Ishihara et al., Macromolecules, 19, 2464 (1986) Mc Knight, A. L .; Chem Rev. 98, 2587, (1998) Z. Hou et al., J. Am. Chem. Soc., 126, 1312 (2004) S. Tanimura et al., Journal of Polymer Science: Part B: Polymer Physics, Vol.39, 973-978 (2001) K. Nomura et al., Macromolecules, 36, 3797 (2003) Adriane G. Simanke et al., Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 40, 471-485 (2002) Pellecchia, C .; Proto, A .; Zambelli, A., Macromolecules, 25, 4450 (1992).

1. An object of the present invention is to provide a novel catalyst composition containing a metallocene complex. Furthermore, this invention makes it a subject to provide the method of manufacturing various high molecular compounds using the said catalyst composition. Preferably, an object of the present invention is to provide a method for producing a novel polymer compound using the catalyst composition.
2. On the other hand, the present invention provides a novel polymer compound. That is, (1) a styrene polymer having a narrow average molecular weight distribution and high syndiotactic, (2) an ethylene-styrene copolymer having a high syndiotactic chain composed of styrene structural units, and (3) regioregularity. And a highly stereoregular 1,3-cyclohexadiene polymer, (4) a copolymer of 1,3-cyclohexadiene and another olefin monomer, and (5) a copolymer of other cyclic olefin. Let it be an issue.

That is, the present invention is as follows.
1stly, this invention is invention of the polymerization catalyst composition shown below.
(1) 1) A central metal M which is a Group 3 metal atom or a lanthanoid metal atom, a ligand Cp ^* containing a substituted or unsubstituted cyclopentadienyl derivative bonded to the central metal, a monoanionic ligand Q ¹ and Q _^2, as well as W number of neutral Lewis bases L, metallocene complex represented by the general formula (I), and 2) a polymerization catalyst composition comprising a non-coordinating anion and the ionic compound comprising a cation .

(2) A feature in which the central metal M in the metallocene complex is scandium Sc, gadolinium Gd, yttrium Y, holmium Ho, lutetium Lu, erbium Er, dysprosium Dy, terbium Tb, and thulium Tm. The catalyst composition as described.
(3) The catalyst composition according to (1), wherein the ligand Cp ^* containing the cyclopentadienyl derivative is a non-bridged ligand.
(4) In (1), the cyclopentadienyl derivative contained in the ligand Cp ^* in the metallocene complex is tetramethyl (trimethylsilyl) cyclopentadienyl or pentamethylcyclopentadienyl. The catalyst composition as described.
(5) at least one of monoanionic ligands Q ¹ and Q ² in the metallocene complex is characterized in that it is a trimethylsilylmethyl group, the catalyst composition according to (1).
(6) The catalyst composition according to (1), wherein the neutral Lewis base L in the metallocene complex is tetrahydrofuran.

2ndly, this invention is invention of the polymerization catalyst composition especially used for the following polymerization reaction among above-described catalyst compositions.
(7) The catalyst composition according to any one of (1) to (6), which is a polymerization catalyst composition of an olefin monomer.
(8) The catalyst composition according to (7), wherein the olefin monomer is selected from the group consisting of unsubstituted styrene, substituted styrene, ethylene, α-olefin, diene, and norbornenes.
(9) The catalyst composition according to any one of (1) to (6), which is a copolymerization catalyst composition of two or more olefin monomers.
(10) The two or more olefin monomers are two or more olefin monomers selected from the group consisting of unsubstituted styrene, substituted styrene, ethylene, α-olefin, diene, and norbornenes. ).

Thirdly, the present invention is an invention of a polymer or copolymer shown below.
(11) A high syndiotactic polymer of substituted or unsubstituted styrene, wherein Mw / Mn, which is an index of molecular weight distribution, is 1.7 or less.
(12) The polymer according to (11), wherein the syndiotacticity is 80 rrrr% or more in pentad display.
(13) A high syndiotactic copolymer of substituted or unsubstituted styrene and substituted styrene, wherein Mw / Mn, which is an index of molecular weight distribution, is 1.7 or less.
(14) The copolymer according to (13), wherein the syndiotacticity is 80 rrrr% or more in pentad display.
(15) A high syndiotactic copolymer of ethylene and substituted or unsubstituted styrene.
(16) The copolymer according to (15), which is a random copolymer and has a syndiotacticity of a chain composed of styrene structural units of 98 r% or more in terms of dyads.
(17) The copolymer according to (15), which is a block copolymer, wherein the syndiotacticity of the styrene block chain is 80 rrrr% or more in pentad display.
(18) The copolymer according to any one of (15) to (17), wherein Mw / Mn, which is an index of molecular weight distribution, is 1.3 or less.
(19) The copolymer according to any one of (15) to (18), wherein the ratio of styrene structural units to all structural units is 5 to 99 mol%.

(20) 1,3-cyclohexadiene polymer, characterized in that the ratio of 1,4-structural units to all structural units is 90% or more and is highly cis-syndiotactic .
(21) The polymer as described in (20), wherein the cis-syndiotacticity is 70 rrrr% or more.
(22) A copolymer of 1,3-cyclohexadiene and substituted or unsubstituted styrene, wherein the ratio of 1,4-structural units to all structural units of 1,3-cyclohexadiene is 90% or more. A featured copolymer.
(23) The copolymer according to (22), which is a random copolymer and has a syndiotacticity of styrene structural units of 98 r% or more in terms of dyads.
(24) A copolymer of 1,3-cyclohexadiene and ethylene.
(25) The copolymer according to (24), wherein the ratio of 1,4-structural units to all structural units of 1,3-cyclohexadiene is 90% or more.
(26) A copolymer of ethylene, norbornene, and substituted or unsubstituted styrene.
(27) The copolymer according to (26), which is a random copolymer and has a syndiotacticity of a chain composed of styrene structural units of 98 r% or more in terms of dyads.
(28) A copolymer of dicyclopentadiene and ethylene having a number average molecular weight of 100,000 or more.
(29) The copolymer according to claim 28, wherein the ratio of dicyclopentadiene structural units to all structural units is 10 mol% or more.

Fourthly, the present invention is an invention of a method for producing a polymer shown below.
(30) A method for producing an olefin polymer, wherein an olefin monomer is polymerized using the polymerization catalyst composition according to any one of (1) to (6).
(31) The production method according to (30), wherein the olefin monomer is selected from the group consisting of substituted and unsubstituted styrene, ethylene, diene, norbornene, and α-olefin.
(32) A method for producing an olefin copolymer, wherein two or more olefin monomers are polymerized using the polymerization catalyst composition according to any one of (1) to (6).
(33) The two or more olefin monomers are two or more olefin monomers selected from the group consisting of substituted and unsubstituted styrene, ethylene, diene, norbornene, and α-olefin. ) Manufacturing method.

(34) The production method according to (30), wherein the olefin polymer is a substituted or unsubstituted styrene polymer, and the olefin monomer is a substituted or unsubstituted styrene.
(35) The production method according to (34), wherein the substituted or unsubstituted styrene polymer is highly syndiotactic.
(36) The production method according to (34), wherein the substituted or unsubstituted styrene polymer is the styrene polymer according to (11) or (12).
(37) The production method according to (32), wherein the olefin copolymer is a styrene copolymer, and the olefin monomer is two or more styrenes selected from substituted and unsubstituted styrene. .
(38) The production method according to (37), wherein the styrene copolymer is highly syndiotactic.
(39) The production method according to (37), wherein the styrene copolymer is the styrene copolymer according to (13) or (14).
(40) The olefin copolymer is a copolymer of ethylene and a substituted or unsubstituted styrene, and the olefin monomer is ethylene and a substituted or unsubstituted styrene. Manufacturing method.
(41) The ethylene / substituted or unsubstituted styrene copolymer is the ethylene / substituted or unsubstituted styrene copolymer according to any one of (15) to (19). (40) The method as described in (40).

(42) The production method according to (30), wherein the olefin polymer is a 1,3-cyclohexadiene polymer, and the olefin monomer is 1,3-cyclohexadiene.
(43) The production method according to (42), wherein the 1,3-cyclohexadiene polymer is the 1,3-cyclohexadiene polymer according to (20) or (21).
(44) The olefin copolymer is a copolymer of 1,3-cyclohexadiene and a substituted or unsubstituted styrene, and the olefin monomer is 1,3-cyclohexadiene and a substituted or unsubstituted styrene. The manufacturing method according to (32).
(45) The production according to (44), wherein the copolymer of 1,3-cyclohexadiene and substituted or unsubstituted styrene is the copolymer according to (22) or (23) Method.
(46) In (32), the olefin copolymer is a copolymer of 1,3-cyclohexadiene and ethylene, and the olefin monomer is 1,3-cyclohexadiene and ethylene. The manufacturing method as described.
(47) The production method according to (46), wherein the copolymer of 1,3-cyclohexadiene and ethylene is the copolymer according to (24) or (25).
(48) The olefin copolymer is a copolymer of ethylene, norbornenes and a substituted or unsubstituted styrene, and the olefin monomer is ethylene, norbornenes and a substituted or unsubstituted styrene. The manufacturing method according to (32).
(49) The production method according to (48), wherein the copolymer is the copolymer according to (26) or (27).
(50) The production method according to (32), wherein the olefin copolymer is a copolymer of dicyclopentadiene and ethylene, and the olefin monomer is dicyclopentadiene and ethylene.
(51) The production method according to (50), wherein the copolymer of cyclopentadiene and ethylene is the copolymer according to (28) or (29).
(52) The production method according to (32), wherein the olefin copolymer is a copolymer of styrene and a conjugated diene, and the olefin monomer is styrene and a conjugated diene.

By using the catalyst composition of the present invention, a new polymerization reaction is provided, and a new method for producing a polymer compound is provided.
In addition, a syndiotactic styrene polymer having a narrow molecular weight distribution, which is one of the polymer compounds produced by using the catalyst composition of the present invention, has higher qualities while having the characteristics of conventional sPS. It can be used as a highly functional sPS.
Furthermore, one of the polymer compounds synthesized by using the catalyst composition of the present invention, an ethylene-styrene copolymer having a high syndiotactic chain composed of styrene structural units has an sPS characteristic. In addition, since the processability is further enhanced, a wider range of applications than sPS is expected.

  On the other hand, various cyclic olefin (co) polymers, which are one of the polymer compounds produced using the catalyst composition of the present invention, are expected to be applied to a wide range of uses as optical materials, for example. .

It is a ¹³ C-NMR spectrum chart of the styrene polymer of the present invention. It is a ¹³ C-NMR spectrum chart of the ethylene-styrene random copolymer of the present invention. It is the figure which expanded and showed a part of spectrum chart of FIG. It is a ¹³ C-NMR spectrum chart of polyethylene, poly (1-hexene), and 1-hexene-ethylene copolymer. It is a ¹³ C-NMR spectrum chart of an ethylene-norbornene copolymer. It is a ¹³ C-NMR spectrum chart of the 1,3-cyclohexadiene polymer obtained in Examples 75, 76, 77, 78, 82 and its enlarged view (excluding Example 75). 6 is a diagram showing a powder X-ray diffraction pattern of a 1,3-cyclohexadiene polymer obtained in Example 77. FIG. ¹ is a ¹ H-NMR spectrum chart of a copolymer of 1,3-cyclohexadiene and styrene obtained in Examples 83 to 88. FIG. ¹³ is a ¹³ C-NMR spectrum chart of a copolymer of 1,3-cyclohexadiene and styrene obtained in Example 85 and an enlarged view thereof. It is a ¹³ C-NMR spectrum chart of the copolymer of 1,3-cyclohexadiene and styrene obtained in Examples 83 to 88. It is a GPC curve of the copolymer of 1, 3- cyclohexadiene and styrene obtained in Examples 83-88. ¹ is a ¹ H-NMR spectrum chart of a copolymer of 1,3-cyclohexadiene and ethylene obtained in Examples 89 to 95. FIG. ¹⁴ is a ¹³ C-NMR spectrum chart and an enlarged view of a copolymer of 1,3-cyclohexadiene and ethylene obtained in Example 92. FIG. ¹³ is a ¹³ C-NMR spectrum chart and an enlarged view of a copolymer of 1,3-cyclohexadiene and ethylene obtained in Examples 89 and 92. 2 is a ¹ H-NMR spectrum chart of an ethylene-norbornene-styrene terpolymer obtained in Example 99. FIG. 10 is a ¹³ C-NMR spectrum chart of an ethylene-norbornene-styrene terpolymer obtained in Example 99. FIG. 2 is a GPC curve of the ethylene-norbornene-styrene terpolymer obtained in Example 99. FIG. 2 is a ¹ H-NMR spectrum chart of a copolymer of dicyclopentadiene and ethylene obtained in Example 102. FIG. 2 is a ¹³ C-NMR spectrum chart of a copolymer of dicyclopentadiene and ethylene obtained in Example 102. FIG. 2 is a GPC curve of a copolymer of dicyclopentadiene and ethylene obtained in Example 102. It is a ¹³ C-NMR spectrum chart of a cyclohexadiene polymer containing 1,4-structural units and 1,2-structural units in a ratio of about 89:11. It is a ¹³ C-NMR spectrum chart of a styrene-isoprene copolymer (70 mol% styrene).

<Catalyst composition of the present invention>
The catalyst composition of the present invention includes a metallocene complex and an ionic compound. Moreover, the other arbitrary components may be included.

1. The metallocene complex contained in the catalyst composition of the present invention The metallocene complex contained in the catalyst composition of the present invention (hereinafter also referred to as “metallocene complex used in the present invention”) is a complex represented by the following general formula (I) It is. The complex is preferably a half metallocene complex.

In general formula (I), M is a central metal in a metallocene complex. The central metal M is a Group 3 metal or a lanthanoid metal, and is not particularly limited. Since the metallocene complex used in the present invention can be used as one component of the polymerization catalyst composition, the central metal M is appropriately selected depending on the type of monomer to be polymerized.
For example, when polymerizing ethylene, any Group 3 metal or lanthanoid metal may be used. For example, as shown in the following examples, scandium Sc, gadolinium Gd, yttrium Y, holmium Ho, Lutetium Lu, erbium Er, dysprosium Dy, terbium Tb, thulium Tm can be selected.
In the case of polymerizing styrene, any Group 3 metal or lanthanoid metal may be used. For example, Sc, Gd, Y, and Lu can be selected as shown in the following examples. it can.

In the general formula (I), Cp ^* is a ligand containing a cyclopentadienyl derivative and is π-bonded to the central metal M. The ligand is preferably a non-bridged ligand. Here, the non-bridged ligand means a ligand having a coordination atom or a coordination group other than the cyclopentadienyl derivative, wherein the cyclopentadienyl derivative is π-bonded to the central metal.
Examples of the cyclopentadienyl derivative contained in Cp ^* include a cyclopentadienyl ring, a condensed ring containing cyclopentadienyl (including but not limited to an indenyl ring and a fluorenyl ring), and the like. The most preferred cyclopentadienyl derivative is a cyclopentadienyl ring.

Cyclopentadienyl ring, represented by the composition formula _{C 5 H 5-X R X} . Here, x represents an integer of 0 to 5. Each R is independently a hydrocarbyl group, a substituted hydrocarbyl group, or a metalloid group substituted with a hydrocarbyl group.

  The hydrocarbyl group is preferably a C 1-20 hydrocarbyl group, more preferably a C 1-20 (preferably C 1-10, more preferably C 1-6) alkyl group, phenyl group, benzyl group, and the like. And most preferably a methyl group.

  The hydrocarbyl group in the substituted hydrocarbyl group is the same as the hydrocarbyl group described above. The substituted hydrocarbyl group is a hydrocarbyl group in which at least one hydrogen atom of the hydrocarbyl group is substituted with a halogen atom, an amide group, a phosphide group, an alkoxy group, an aryloxy group, or the like.

  Examples of the metalloid in the metalloid group substituted with the hydrocarbyl group include germyl Ge, stannyl Sn, silyl Si and the like. The hydrocarbyl group substituted with a metalloid group is the same as the hydrocarbyl group described above, and the number of substitutions is determined by the type of metalloid (for example, in the case of a silyl group, the number of substitutions of the hydrocarbyl group is 3).

  Preferably, at least one R of the cyclopentadienyl ring is a metalloid group (preferably a silyl group) substituted with a hydrocarbyl group, more preferably a trimethylsilyl group.

  Specific examples of preferred cyclopentadienyl rings include, but are not limited to, those represented by the following structural formulas.

The cyclopentadienyl derivative contained in the ligand Cp ^* may be an indenyl ring (composition formula: C ₉ H _7-x R _x ) or a tetrahydroindenyl ring (composition formula: C ₉ H _11-x R _x ). Good. Here, R is the same as R in the above-described cyclopentadienyl ring, and X is an integer of 0 to 7 or 0 to 11.

The cyclopentadienyl derivative contained in the ligand Cp ^* is a fluorenyl ring (composition formula: C ₁₃ H _9-x R _x ) or octahydrofluorenyl ring (composition formula: C ₁₃ H _17-x R _x ). Etc. Here, R is the same as R in the above-described cyclopentadienyl ring, and X is an integer of 0-9 or 0-17.

In the complex represented by the general formula (I) used in the present invention, Q ¹ and Q ² are the same or different monoanionic ligands. As monoanionic ligands, 1) hydride, 2) halide, 3) substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, 4) alkoxy group or aryloxy group, 5) amide group, or 6) Examples include, but are not limited to, phosphino groups.
Q ¹ and Q ² may be bonded to each other or may be combined to form a so-called dianionic ligand. Examples of dianionic ligands include alkylidene, dienes, cyclometallated hydrocarbyl groups, and bidentate chelate ligands.

The halide may be any of chloride, bromide, fluoride, and iodide.
The hydrocarbyl group having 1 to 20 carbon atoms is preferably a methyl group, ethyl group, propyl group, butyl group, amyl group, isoamyl group, hexyl group, isobutyl group, heptyl group, octyl group, nonyl group, decyl group, cetyl group. In addition to an alkyl group such as a 2-ethylhexyl group, an unsubstituted hydrocarbyl group such as a phenyl group or a benzyl group, a substituted hydrocarbyl group such as a substituted benzyl group, a trialkylsilylmethyl group or a bis (trialkylsilyl) methyl group may be used. . Examples of preferred hydrocarbyl groups include substituted or unsubstituted benzyl groups and trialkylsilylmethyl groups, and more preferred examples include ortho-dimethylaminobenzyl groups and trimethylsilylmethyl groups.
The alkoxy group or aryloxy group is preferably a methoxy group, a substituted or unsubstituted phenoxy group, and the like.
The amide group is preferably a dimethylamide group, a diethylamide group, a methylethylamide group, a di-t-butylamide group, a diisopropylamide group, an unsubstituted or substituted diphenylamide group, and the like.
The phosphino group is preferably a diphenylphosphino group, a dicyclohexylphosphino group, a diethylphosphino group, a dimethylphosphino group, or the like.

The alkylidene is preferably methylidene, ethylidene, propylidene or the like.
The cyclometallated hydrocarbyl group is preferably propylene, butylene, pentylene, hexylene, octylene and the like.
The diene is preferably 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,4-dimethyl-1, 3-pentadiene, 2-methyl-1,3-hexadiene, 2,4-hexadiene, and the like.

In the complex represented by the general formula (I) used in the present invention, L is a neutral Lewis base. Neutral Lewis bases include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride and the like.
L may be bonded to Q ¹ and / or Q ² to form a so-called multidentate ligand.

W of _{L W} in the general formula (I) represents the number of neutral Lewis bases L. w is an integer of 0 to 3, preferably 0 to 1.

The metallocene complex used in the present invention can be prepared by the method described above, for example, (1) Tardif, O .; Nishiura, M .; Hou, ZM Organometallics 22, 1171, (2003), or (2) Hultzsch, KC; Spaniol, TP; Okuda, J. Angew. Chem. Int. Ed, 38, 227, (1999).
Specific examples of methods for producing these complexes are also described in Reference Examples described later.

2. Ionic compound contained in catalyst composition of the present invention As described above, the catalyst composition of the present invention contains an ionic compound. Here, the ionic compound includes an ionic compound composed of a non-coordinating anion and a cation. The ionic compound is combined with the metallocene complex described above to cause the metallocene complex to exhibit activity as a polymerization catalyst. As the mechanism, it can be considered that the ionic compound reacts with the metallocene complex to generate a cationic complex (active species).

  As the non-coordinating anion which is a constituent component of the ionic compound, for example, a tetravalent boron anion is preferable, and tetra (phenyl) borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (tri Fluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) Examples thereof include borate, [tris (pentafluorophenyl), phenyl] borate, and tridecahydride-7,8-dicarbaoundecaborate.

  Of these non-coordinating anions, tetrakis (pentafluorophenyl) borate is preferred.

Examples of the cation that is a constituent component of the ionic compound include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal.
Specific examples of the carbonium cation include a tri-substituted carbonium cation such as a triphenylcarbonium cation and a tri-substituted phenylcarbonium cation. Specific examples of the tri-substituted phenyl carbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation.
Specific examples of ammonium cations include trialkylammonium cations, triethylammonium cations, tripropylammonium cations, tributylammonium cations, tri (n-butyl) ammonium cations, and the like, N, N-dimethylanilinium cations, N Dialkyl ammonium cations such as N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, N, N-dialkylanilinium cation, di (isopropyl) ammonium cation, dicyclohexylammonium cation, etc. included.
Specific examples of the phosphonium cation include triarylphosphonium cations such as a triphenylphosphonium cation, a tri (methylphenyl) phosphonium cation, and a tri (dimethylphenyl) phosphonium cation.

  Among these cations, an anilinium cation or a carbonium cation is preferable, and a triphenylcarbonium cation is more preferable.

That is, the ionic compound contained in the catalyst composition of the present invention may be a combination of those selected from the above-mentioned non-coordinating anions and cations.
Preferably, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocete Examples thereof include nium tetrakis (pentafluorophenyl) borate. One ionic compound may be used, or two or more ionic compounds may be used in combination.

  Among these ionic compounds, particularly preferred are triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like.

In addition, B (C ₆ F ₅ ) ₃ , Al (C ₆ F ₅ ) _3, etc., which are Lewis acids that can react with transition metal compounds to form cationic transition metal compounds, are used as ionic compounds. These may be used in combination with the ionic compound.
Furthermore, an alkylaluminum compound (aluminoxane, preferably MAO or MMAO), or a combination of an alkylaluminum compound and a borate compound can also be used as the ionic compound, or may be used in combination with other ionic compounds. . In particular, when the monoanionic ligand Q of the complex (general formula (I)) used in the present invention is other than alkyl or hydride (for example, a halogen), an alkylaluminum compound or an alkylaluminum compound It may be preferable to use a combination of borate compounds.

3. Other optional components contained in the catalyst composition of the present invention The catalyst composition of the present invention may contain optional components in addition to the metallocene complex and the ionic compound. Examples of the optional component include alkyl aluminum compounds, silane compounds, hydrogen and the like.
The alkylaluminum compound usually includes an organoaluminum compound called aluminoxane (alumoxane) used in a metallocene polymerization catalyst. For example, methylaluminoxane (MAO) etc. are mentioned.
Examples of the silane compound include phenylsilane.

4). As described above, the catalyst composition of the present invention includes the metallocene complex and an ionic compound. In the catalyst composition of the present invention, the molar ratio of the ionic compound to the metallocene complex varies depending on the type of the complex and the ionic compound.
The molar ratio is, for example, 0.5 to 1 when the ionic compound is composed of a carbonium cation and a boron anion (for example, [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]). In the case of MAO or the like, it is preferably about 300 to 4000.
Since the ionic compound is considered to be a catalytically active species by ionizing, that is, cationizing, the metallocene complex, it is considered that the metallocene complex cannot be sufficiently activated when the ratio is not more than the above-described ratio.
On the other hand, if an ionic compound composed of a carbonium cation and a boron anion is present in excess, there is a possibility that they may react with a monomer to be polymerized.

  Usually, since it is considered that the Lewis acid L may inhibit the coordination to the active center of the olefin monomer, the complex represented by the general formula (I) where w = 0 is preferable as the complex used in the present invention. Can also be considered.

The catalyst composition of the present invention can be used as a polymerization catalyst composition (particularly an addition polymerization catalyst composition).
For example, 1) providing a composition containing each component (such as a metallocene complex and an ionic compound) in the polymerization reaction system, or 2) providing each component separately in the polymerization reaction system, By constituting the composition, it can be used as a polymerization catalyst composition.
In the above 1), “providing as a composition” includes providing a metallocene complex (active species) activated by reaction with an ionic compound.

As described above, the catalyst composition of the present invention can be used as a polymerization catalyst composition in polymerization reactions of various monomers. Examples of the polymerization reaction in which the catalyst composition of the present invention can act as a catalyst include polymerization reactions of arbitrary monomer compounds that are known to have addition polymerizability. For example, olefin monomers, epoxy monomers, and isocyanate monomers. Examples thereof include polymerization reactions of monomers, lactone monomers, lactide monomers, cyclic carbonate monomers, alkyne monomers, and the like. Preferably, a polymerization reaction of an olefin monomer, particularly preferably a polymerization reaction of α-olefin, styrene, ethylene, diene, cyclic olefin (including norbornenes such as 2-norbornene and dicyclopentadiene and cyclohexadiene), and the like. .
Examples of dienes that are olefinic monomers include 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2 , 4-dimethyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 2,4-hexadiene, and cyclic dienes such as cyclohexadiene.

  The polymerization catalyst composition of the present invention can be used not only as a homopolymerization reaction but also as a polymerization catalyst composition in a copolymerization reaction. The monomer to be copolymerized is sufficient if it has addition polymerizability, preferably two or more olefinic monomers, particularly preferably two or more selected from α-olefin, substituted and unsubstituted styrene, ethylene, diene, and cyclic olefin. Monomer.

<Polymer compound of the present invention>
One aspect of the polymer compound of the present invention is a highly syndiotactic polymer of unsubstituted or substituted styrene, or a highly syndiotactic copolymer of two or more styrenes selected from unsubstituted styrene and substituted styrene. Characterized by a narrow molecular weight distribution (hereinafter each referred to as “the styrene polymer of the present invention” or “the styrene copolymer of the present invention”, both of which are referred to as “the styrene (co) polymer of the present invention”. May be collectively referred to as “union”).
One aspect of the polymer compound of the present invention is an ethylene-styrene copolymer, characterized in that the stereoregularity of a chain composed of styrene structural units is highly syndiotactic (hereinafter referred to as “the present invention”). Also referred to as “ethylene-styrene copolymer”).

One aspect of the polymer compound of the present invention is a 1,3-cyclohexadiene polymer, which has a high ratio of 1,4-structural units to all structural units and is a high cis-syndiotactic polymer. (Hereinafter also referred to as “the CHD polymer of the present invention”).
One embodiment of the polymer compound of the present invention is a copolymer of 1,3-cyclohexadiene and another olefin. An example thereof is a copolymer of 1,3-cyclohexadiene and substituted or unsubstituted styrene, characterized in that the ratio of 1,4-structural units to the total structural units of 1,3-cyclohexadiene is high. (Hereinafter, also referred to as “CHD-ST copolymer of the present invention”). Another example is a copolymer of 1,3-cyclohexadiene and ethylene (hereinafter, also referred to as “CHD-ET copolymer of the present invention”).
One embodiment of the polymer compound of the present invention is a copolymer of norbornenes, ethylene, and substituted or unsubstituted styrene (hereinafter, also referred to as “NBE-ET-ST copolymer of the present invention”).
One embodiment of the polymer compound of the present invention is a copolymer of dicyclopentadiene and ethylene, and has a specific molecular weight (hereinafter referred to as “the DCPD-ET copolymer of the present invention”). Called).

1. The Styrene Polymer or Styrene Copolymer of the Present Invention The styrene polymer or styrene copolymer (styrene (co) polymer) of the present invention has a substituent (R) on the phenyl ring represented by the following formula (A). A polymer containing styrene repeating units with or without _n . The repeating unit represented by the formula (A) is usually repeated with a head-to-tail bond. The repeating unit represented by the formula (A) contained in the styrene (co) polymer of the present invention may be one type (homopolymer) or two or more types (copolymer).

R on the phenyl ring in the formula (A) is an arbitrary substituent or atom, and examples thereof include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylsilyl group, and a carboxyalkyl. Group and the like.
The phenyl ring of the styrene structural unit of the styrene (co) polymer of the present invention has n Rs. Preferably, n = 0 to 3, and more preferably n = 0 or 1. Most preferably, n = 0 or n = 1, and R is bonded to the phenyl ring carbon in the para position with respect to the phenyl ring carbon bonded to the polymer main chain.

Examples of the substituent or atom (R) _n include, but are not limited to, the following.
1) Alkyl such as p-methyl, m-methyl, o-methyl, 2,4-dimethyl, 2,5-dimethyl, 3,4-dimethyl, 3,5-dimethyl, p-tertiary butyl, etc. 2) p- Halogens such as chloro, m-chloro, o-chloro, p-bromo, m-bromo, o-bromo, p-fluoro, m-fluoro, o-fluoro, o-methyl-p-fluoro 3) p-chloromethyl Halogen substituted alkyl such as m-chloromethyl, o-chloromethyl 4) alkoxy such as p-methoxy, m-methoxy, o-methoxy, p-ethoxy, m-ethoxy, o-ethoxy 5) p-carboxymethyl, Carboxyalkyl such as m-carboxymethyl and o-carboxymethyl 6) Alkylsilyl such as p-trimethylsilyl

The styrene (co) polymer of the present invention is a stereoregular polymer and a highly syndiotactic polymer. Here, high syndiotactic means a ratio in which the phenyl rings in the repeating units represented by the adjacent formula (A) are alternately arranged with respect to the plane formed by the polymer main chain (this ratio is referred to as “syndiotactic”). It is called “City”.
The syndiotacticity of the styrene (co) polymer of the present invention is 80 rrrr% (preferably 85 rrrr%, more preferably 90 rrrr%, particularly preferably 95 rrrr%, most preferably 99 rrrr%) in pentad. These syndiotacticities can be calculated from data obtained by measuring NMR (particularly ¹³ C-NMR) of the styrene (co) polymer of the present invention. This calculation has been specifically described in Examples described later.

The styrene (co) polymer of the present invention is characterized by a narrow molecular weight distribution. Here, the molecular weight distribution means a value (Mw / Mn) measured by a GPC method (measured at 145 ° C. using polystyrene as a standard substance and 1,2-dichlorobenzene as an eluent). For example, a GPC measuring apparatus (TOSOH HLC 8121 GPC / HT).
Here, the narrow molecular weight distribution usually means that Mw / Mn = 1.7 or less, preferably 1.6 or less, more preferably 1.5 or less, and most preferably 1.4 or less. .

The number average molecular weight of the styrene (co) polymer of the present invention is arbitrary, but the unsubstituted styrene polymer is preferably 0.4 × 10 ⁴ or more, more preferably 8.5 × 10 ⁴ or more, and further Preferably it is 20.0 × 10 ⁴ or more, most preferably 25.0 × 10 ⁴ or more.

  The melting point of the polystyrene of the present invention is usually 260 ° C. or higher. The melting point can be measured by a differential scanning calorimetry (DSC) method.

  The styrene (co) polymer of the present invention has the same characteristics as the conventionally known syndiotactic styrene (co) polymer (sPS), that is, has a high melting point, heat resistance and chemical resistance. Since it has characteristics such as dimensional stability, it can be used as various engineer plastics. Furthermore, due to the property that the molecular weight distribution is sharp, it is expected to be used as a higher quality engineering plastic.

2. Ethylene-styrene copolymer of the present invention The ethylene-styrene copolymer of the present invention comprises a structural unit derived from styrene represented by the following formula (A) and a structural unit derived from ethylene represented by the formula (B). It is a copolymer having. The structural unit represented by the formula (A) may be one type, but may be two or more types.
Here, R and n in the formula (A) are the same as R and n described in the formula (A) which is a repeating unit in the styrene (co) polymer.

  In the ethylene-styrene copolymer of the present invention, the structural units represented by the above formulas (A) and (B) may be arranged in any order. That is, both may be arranged at random, or arranged with some regularity (for example, the structural units of (A) and (B) are arranged alternately, and each is arranged to some extent continuously. May be arranged in any other order). Accordingly, the ethylene-styrene copolymer of the present invention may be a random copolymer, an alternating copolymer, a block copolymer, or other ordered copolymer. The ethylene-styrene copolymer of the present invention is preferably a random copolymer or a block copolymer.

  The ethylene-styrene copolymer of the present invention is characterized by having stereoregularity. That is, when the structural unit represented by the formula (A) contained in the copolymer is continuous, the phenyl ring of the structural unit of the continuous formula (A) is on the plane formed by the polymer main chain. It is characterized by a high ratio (syndiotacticity) of alternating arrangement.

Here, the syndiotacticity in the ethylene-styrene copolymer, which is a random copolymer, is the total of two continuous units (dyads) of the structural unit represented by the formula (A) in the copolymer. It means the ratio (indicated by “r%”) of dyads having a syndiotactic sequence (sequence in which phenyl groups are alternately arranged with respect to the polymer main chain).
In the ethylene-styrene copolymer which is a random copolymer of the present invention, the syndiotacticity of a chain composed of the structural unit of the formula (A) is 60 r% or more, preferably 80 r% or more, more preferably in terms of dyad display. Is 98 r% or more.

The syndiotacticity in the ethylene-styrene copolymer that is the random copolymer can be calculated from a ¹³ C-NMR spectrum. In the examples described later, the calculation has been specifically described.

On the other hand, syndiotacticity in an ethylene-styrene copolymer that is a block copolymer is a styrene block chain in the copolymer (a block chain in which the structural unit represented by the formula (A) is repeated). Of all five continuous units (pentads) in the case of pentad that are syndiotactic (arranged in which phenyl groups are alternately arranged with respect to the polymer main chain) (indicated by “rrrr%”) Mean).
The ethylene-styrene copolymer, which is a block copolymer of the present invention, has a syndiotacticity of styrene block chain of 80 rrrr%, preferably 85 rrrr%, more preferably 90 rrrr%, particularly preferably 95 rrrr% in terms of pentad. Most preferably, it is 99 rrrr% or more.

  The syndiotacticity in the ethylene-styrene copolymer, which is the block copolymer, can be determined in the same manner as the syndiotacticity of the styrene (co) polymer of the present invention described above (that is, determined from the NMR spectrum). be able to).

The content of the structural unit of the formula (A) and the structural unit of the formula (B) contained in the ethylene-styrene copolymer of the present invention is arbitrary. For example, among all the structural units, the structural unit of the formula (A) can be 5 to 99 mol% in terms of molar ratio.
When the content of the structural unit of the formula (A) increases, the stereoregularity of the arrangement of the structural unit of the formula (A) (structural unit derived from styrene), which is a feature of the ethylene-styrene copolymer of the present invention, is high ( High syndiotactic characteristics can be effectively exhibited. That is, the ethylene-styrene copolymer of the present invention can be imparted with heat synergistic polystyrene characteristics such as heat resistance, chemical resistance, and dimensional stability.
On the other hand, since the ethylene-styrene copolymer of the present invention contains a structural unit derived from ethylene of the formula (B), the difficulty of molding processing that the conventional syndiotactic polystyrene had has been reduced.

The molecular weight distribution of the ethylene-styrene copolymer of the present invention is arbitrary, but can be a copolymer having a relatively narrow molecular weight distribution. Here, the molecular weight distribution means a value (Mw / Mn) measured by a GPC method (measured at 145 ° C. using polystyrene as a standard substance and 1,2-dichlorobenzene as an eluent). For example, a GPC measuring apparatus (TOSOH HLC 8121 GPC / HT).
The molecular weight distribution of the ethylene-styrene copolymer of the present invention is usually such that its index Mw / Mn is 4.0 or less, preferably 2.0 or less, and more preferably 1.3 or less.

The number average molecular weight of the ethylene-styrene copolymer of the present invention is arbitrary, but if it is an ethylene-unsubstituted styrene copolymer, it is usually 1.0 × 10 ⁴ or more, preferably 8.0 × 10 ⁴ or more. More preferably, it is 50.0 × 10 ⁴ or more.

  The melting point of the ethylene-styrene copolymer of the present invention varies depending on the structure of the structural unit derived from styrene, the ratio of the structural unit derived from styrene to the structural unit derived from ethylene, and others. The ethylene-styrene copolymer of the present invention having a melting point of 200 ° C. or higher is expected to have the same characteristics (heat resistance, chemical resistance, dimensional stability, etc.) as conventional sPS. Here, the melting point is a melting point measured by a differential scanning calorimetry (DSC) method.

3. Conjugated diene-styrene copolymer produced by the production method of the present invention The conjugated diene-styrene copolymer produced by the production method of the present invention will be described by taking an isoprene-styrene copolymer as an example. The isoprene-styrene copolymer produced by the production method of the present invention (hereinafter, “isoprene-styrene copolymer in the present invention”) is a structural unit derived from styrene represented by the following formula (A) and a formula ( It is a copolymer having one or more structural units derived from isoprene represented by C1) to (C4). The structural unit represented by the formula (A) may be one type, but may be two or more types. The main unit of the structural unit derived from isoprene is the structural unit represented by (C1) (for example, 60% or more of all structural units derived from isoprene).

  In the isoprene-styrene copolymer in the present invention, the structural units represented by the formula (A) and the formulas (C1) to (C4) may be arranged in an arbitrary order. That is, each structural unit may be arranged at random or may be arranged with some regularity. Therefore, the isoprene-styrene copolymer in the present invention may be a random copolymer, an alternating copolymer, a block copolymer, or other ordered copolymer, preferably a random copolymer or A block copolymer, more preferably a random copolymer.

The isoprene-styrene copolymer in the present invention preferably has stereoregularity. That is, when the structural unit represented by the formula (A) contained in the copolymer is continuous, the phenyl ring of the structural unit of the continuous formula (A) is on the plane formed by the polymer main chain. It is preferable that the ratio (syndiotacticity) of alternating arrangement is high.
On the other hand, the tacticity of the structural units represented by the formulas (C1) to (C4) is not particularly limited, and is, for example, atactic.

  Of all two continuous units (dyads) of the structural unit represented by the formula (A) in the isoprene-styrene copolymer that is a random copolymer, the proportion of dyads that are syndiotacticly arranged (“r% ] Is 60 r% or more, preferably 80 r% or more, more preferably 98 r% or more.

The syndiotacticity in the isoprene-styrene copolymer that is a random copolymer can be calculated from ¹³ C-NMR.

  The ratio of the structural unit represented by the formula (A) and the structural unit represented by the formulas (C1) to (C4) contained in the isoprene-styrene copolymer in the present invention is arbitrary. For example, among all the structural units, the molar ratio of the structural unit of the formula (A) can be 5 to 90 mol%.

  The molecular weight distribution of the isoprene-styrene copolymer in the present invention is arbitrary. For example, the index Mw / Mn may be 1.8 or less, preferably 1.2 or less. The molecular weight distribution is measured by a method similar to the method for measuring the molecular weight distribution of the ethylene-styrene copolymer described above.

  The number average molecular weight of the isoprene-styrene copolymer in the present invention is arbitrary, but it is usually 30,000 or more, preferably 100,000 or more if it is an isoprene-unsubstituted styrene copolymer.

  The melting point of the isoprene-styrene copolymer in the present invention varies depending on the structure of the structural unit derived from styrene, the ratio of each structural unit, etc., but is usually about 250 ° C.

3. 1,3-cyclohexadiene polymer of the present invention The 1,3-cyclohexadiene polymer (CHD polymer) of the present invention is characterized by a high ratio of 1,4-structural units to all structural units contained therein. To do. That is, the CHD polymer may contain 1,4-structural units and 1,2-structural units depending on the bonding mode, as shown by the following formula, but the 1,4-structural units of the CHD polymer of the present invention are 1,4- It is characterized by a high ratio of structural units. A high ratio of 1,4-structural units means that {1,4-structural unit number / (1,4-structural unit number + 1,2-structural unit number)} is 80% or more, preferably 90% or more, More preferably, it means 95% or more, more preferably 99% or more.

The ratio of 1,4-structural units to all structural units of the CHD polymer of the present invention can be determined from ¹³ C-NMR spectral data. That is, the olefin carbon peak of the 1,2-polymer unit of the CHD polymer is observed near 128 ppm, whereas the olefin carbon peak of the 1,4-structure unit is observed near 132 ppm (see FIG. 21). Therefore, the peak areas of both may be compared.

The CHD polymer of the present invention is characterized by a high ratio of 1,4-structural units to all structural units, but is a stereoregular polymer and a high cis-syndiotactic polymer. It is characterized by that.
That is, in general, a bicontinuous unit (dyad) of 1,4-structural units contained in a CHD polymer can be the following four geometric isomers. In contrast, the CHD polymer of the present invention has a ratio of cis-syndiotactic bicontinuous units to all bicontinuous units of 1,4-structural units contained therein (referred to as “cis-syndiotacticity”). Is characterized by high.

  Specifically, the cis-syndiotacticity of the CHD polymer of the present invention is usually 70 rrrr% or more, preferably 80 rrrr% or more, more preferably 90 rrrr% or more, and most preferably 99 rrrr% or more. It is.

The cis-syndiotacticity of the CHD polymer of the present invention can be measured by analyzing a ¹³ C-NMR spectrum or a powder X-ray diffraction pattern.
As shown in the enlarged views of FIGS. 6 and 21, in the ¹³ C-NMR spectrum of the 1,3-cyclohexadiene polymer, the tertiary carbon signal connecting the 1,3-cyclohexadiene units has multiple peaks. Is known to appear around 39-41 ppm. Furthermore, the peak at 40.7 ppm has an all-trans structure, and the remaining peak has an all-cis or cis-trans structure (see Z. Sharaby et al., Macromolecules, 15, 1167-1173 (1982)). .
Further, as described in Non-Patent Document 7 (Journal of Polymer Science: Part B: Polymer Physics, Vol. 39, 973-978 (2001)), a cis-syndiotactic polymer and a cis-isotactic polymer are used. Although the powder X-ray diffraction patterns of the powders of cis-syndiotactic are the same, the structure of cis-syndiotactic is more stable than that of cis-isotactic. However, it is considered that even when the cis-syndiotactic polymer is subjected to annealing, the structure does not change and the diffraction pattern does not change (these are described in detail in Non-Patent Document 7).
As shown in FIG. 7, the powder of the CHD polymer of the present invention (polymer obtained in Example 72) was subjected to powder X-ray diffraction before and after being annealed (at 227 ° C., heated in an argon atmosphere for 30 minutes). The pattern does not change.

  From these facts, the 39.9 ppm peak is attributed to rrrr (cis-syndiotactic) and the 40.1 ppm peak is attributed to rr.

  The cis-syndiotacticity of the CHD polymer of the present invention is determined by the types of ligands and central metals of metallocene complexes, anions and cations of ionic compounds contained in the catalyst composition used in the production (described later). It is possible to control by appropriately selecting the type, reaction temperature, reaction solvent and the like.

The molecular weight distribution of the CHD polymer of the present invention is not particularly limited, but usually the index Mw / Mn is 2.6 or less, preferably 2.0 or less.
Here, the molecular weight distribution means a value (Mw / Mn) measured by a GPC method (measured at 145 ° C. using polystyrene as a standard substance and 1,2-dichlorobenzene as an eluent). For example, a GPC measuring apparatus (TOSOH HLC 8121 GPC / HT).

The molecular weight of the CHD polymer of the present invention is not particularly limited, but the number average molecular weight is preferably 7000 or less. The lower limit is not particularly limited, but may be 1000 or more.
The number average molecular weight can be measured by the GPC method similar to the molecular weight distribution.

  The CHD polymer of the present invention usually has a melting point. The temperature of the melting point is not particularly limited, but is usually about 220 to 250 ° C. Here, the melting point is a melting point measured by a differential scanning calorimetry (DSC) method.

4). Copolymer of 1,3-cyclohexadiene and substituted or unsubstituted styrene of the present invention (CHD-ST copolymer)
The copolymer of 1,3-cyclohexadiene and substituted or unsubstituted styrene of the present invention is a polymer containing (preferably consisting of) a 1,3-cyclohexadiene structural unit and a styrene structural unit. Here, the content of the 1,3-cyclohexadiene structural unit in the CHD-ST copolymer of the present invention can be arbitrarily selected and can be controlled in the range of approximately 0 mol% to approximately 100 mol%.
The content can be measured by ¹ H-NMR. For example, as shown in FIG. 8, the peak derived from olefin hydrogen of the cyclohexadiene structural unit is in the vicinity of about 5.2 to 6.0 ppm, and the peak of aromatic hydrogen of the styrene structural unit is about 6.7 to 7. Since it is in the vicinity of 4 ppm, it may be obtained from the ratio of both peaks.
The content is controlled by adjusting the ratio of each monomer as a raw material in the production of the CHD-ST copolymer.

  As described above, the CHD-ST copolymer of the present invention includes a 1,3-cyclohexadiene structural unit and a styrene structural unit, and both structural units may be arranged in an arbitrary order. That is, both of them may be arranged at random, or arranged with some regularity (for example, both structural units are arranged alternately, each of them is arranged to some extent continuously, or arranged in a fixed order. You may). Therefore, the CHD-ST copolymer of the present invention may be a random copolymer, an alternating copolymer, a block copolymer, or other ordered copolymer, preferably a random copolymer or A block copolymer, more preferably a random copolymer.

The CHD-ST copolymer of the present invention is characterized in that the ratio of 1,4-structural units to the total structural units of 1,3-cyclohexadiene contained therein is high. The ratio of the 1,4-structural units is usually 80% or more, preferably 90% or more, more preferably 95% or more, and further preferably 99% or more. The ratio of 1,4-structural units can be measured by the same method as the method for measuring the ratio of 1,4-structural units in the aforementioned 1,3-cyclohexadiene polymer.
Furthermore, it is preferable that the chain | strand which consists of a 1, 4- structural unit of 1, 3- cyclohexadiene contained in the CHD-ST copolymer of this invention is a high cis-syndiotactic. Specifically, the cis-syndiotacticity of 2,4-unit continuous units of 1,3-cyclohexadiene is usually 50 r% or more, more preferably 70 r% or more, and even more preferably 90 r% or more. It is. This cis-syndiotacticity can be measured by the same method as the method for measuring cis-syndiotacticity in the aforementioned 1,3-cyclohexadiene polymer.

The styrene structural unit contained in the CHD-ST copolymer of the present invention is represented by the following formula (A). Here, the substituent (R) _n on the phenyl ring may or may not be present. When the structural units represented by formula (A) are continuously arranged, they are usually head-to-tail bonded. The styrene structural unit contained in the CHD-ST copolymer of the present invention may be one type, but may be two or more types.
R and n in the following formula (A) are not particularly limited, but are the same as R and n described in formula (A) which is a repeating unit in the styrene (co) polymer.

In the CHD-ST copolymer of the present invention, it is preferred that the chain composed of styrene structural units contained therein is highly syndiotactic. Specifically, the CHD-ST copolymer of the present invention, which is a random copolymer, is a syndiotactic array of all two continuous units (dyads) of styrene structural units contained therein. The ratio (syndiotacticity) is usually 60 r% or more, preferably 80 r% or more, more preferably 98 r% or more. The syndiotacticity of the chain composed of styrene structural units was determined in the same manner as the method for measuring the syndiotacticity of the chain composed of styrene structural units in the ethylene-styrene copolymer (analysis of ¹³ C-NMR spectrum). Can be measured).

  Mw / Mn, which is an index of molecular weight distribution of the CHD-ST copolymer of the present invention, is usually 2 or less, preferably 1.8 or less. The molecular weight distribution means a value (Mw / Mn) measured by a GPC method (measured at 40 ° C. using polystyrene as a standard substance and tetrahydrofuran as an eluent), for example, using a GPC measuring apparatus (TOSOH HLC 8220 GPC). Can be measured.

  The molecular weight of the CHD-ST copolymer of the present invention is not particularly limited, but the number average molecular weight is usually 10,000 or less, preferably 8,000 or less. Although a minimum is not specifically limited, What is necessary is just to set it as 1000 or more (preferably 3000 or more). The molecular weight is related to the content of the 1,3-cyclohexadiene structural unit, and the molecular weight tends to increase as the content decreases. The molecular weight can be measured by the GPC method similar to the measurement of the molecular weight distribution.

  The CHD-ST copolymer of the present invention usually has a glass transition temperature. The glass transition temperature is not particularly limited, but is usually 100 ° C. or higher (preferably 150 ° C. or higher). The glass transition temperature is measured by a differential scanning calorimetry (DSC) method.

5. Copolymer of 1,3-cyclohexadiene and ethylene of the present invention (CHD-ET copolymer)
The copolymer of 1,3-cyclohexadiene and ethylene of the present invention is a polymer containing (preferably consisting of) a 1,3-cyclohexadiene structural unit and an ethylene structural unit. Here, the content of the 1,3-cyclohexadiene structural unit in the CHD-ET copolymer of the present invention can be arbitrarily selected, but is usually 3 to 70 mol%.
This content rate can be calculated | required from a < ¹ > H-NMR spectrum. For example, as shown in FIG. 12, the peak area of a peak around 5.3 to 5.8 ppm attributed to olefin hydrogen of a 1,3-cyclohexadiene structural unit, and the peak areas of other peaks It can be obtained from the ratio.
As will be described later, the content can be controlled by adjusting the amount of 1,3-cyclohexadiene in the monomer used as a raw material.

  As described above, the CHD-ET copolymer of the present invention includes a 1,3-cyclohexadiene structural unit and an ethylene structural unit, and both structural units may be arranged in an arbitrary order. That is, both of them may be arranged at random, or arranged with some regularity (for example, both structural units are arranged alternately, each of them is arranged to some extent continuously, or arranged in a fixed order. You may). Therefore, the CHD-ET copolymer of the present invention may be a random copolymer, an alternating copolymer, a block copolymer, or other ordered copolymer, preferably a random copolymer or A block copolymer, more preferably a random copolymer.

The 1,3-cyclohexadiene structural unit contained in the CHD-ET copolymer of the present invention may be a 1,4-structural unit or a 1,2-structural unit, but the ratio of 1,4-structural units {1, 4-structural unit number / (1,4-structural unit number + 1,2-structural unit number)} is usually 80% or more, preferably 90% or more, more preferably 95% or more, Preferably, it is 99% or more. The ratio can be determined from a ¹ H-NMR spectrum, and specifically, can be measured by the same method as the method for measuring the ratio of 1,4-structural units in the CHD polymer described above.
Furthermore, the chain composed of 1,4-structural units of 1,3-cyclohexadiene in the CHD-ET copolymer of the present invention is preferably highly cis-syndiotactic. Specifically, the cis-syndiotacticity of two consecutive units of 1,4-cyclohexadiene in the 1,4-structural unit is usually 50 r% or more, preferably 70 r% or more, more preferably 90 r. % Or more. The cis-syndiotacticity can be measured by the same method as the above-described method for measuring the cis-syndiotacticity of the CHD polymer.

  The molecular weight distribution of the CHD-ET copolymer of the present invention is not particularly limited, but its index Mw / Mn is usually 1.7 or less, preferably 1.4 or less. The molecular weight distribution means a value (Mw / Mn) measured by the GPC method (measured at 145 ° C. using polystyrene as a standard substance and 1,2-dichlorobenzene as an eluent). For example, a GPC measuring device (TOSOH HLC 8121 GPC / HT).

The molecular weight of the CHD-ET copolymer of the present invention is not particularly limited, but the number average molecular weight is usually 3 × 10 ⁵ or less, preferably 2 × 10 ⁵ or less. Although a minimum is not specifically limited, What is necessary is just 1000 or more. The molecular weight is related to the content of structural units derived from 1,3-cyclohexadiene. The lower the content, the higher the molecular weight. The molecular weight can be determined by the GPC method similar to the molecular weight distribution. Further, the molecular weight can be increased by increasing the temperature of the polymerization reaction in the production of the CHD-ET copolymer.

  The CHD-ET copolymer of the present invention usually has a melting point. The temperature of the melting point is not particularly limited, but is usually about 120 to 130 ° C. The melting point is measured by a differential scanning calorimetry (DSC) method.

6). Copolymers of norbornenes, ethylene and styrene of the present invention (NBE-ET-ST copolymer)
The copolymer of norbornenes / ethylene / styrene of the present invention means a polymer containing (preferably consisting of) such norbornene structural units, ethylene structural units, and styrene structural units. Preferably, the NBE-ET-ST copolymer of the present invention is a terpolymer.
The norbornenes, ethylene and styrene structural units in the NBE-Et-ST copolymer of the present invention may be arranged in any order. That is, each structural unit may be arranged at random, or may be arranged with some regularity (for example, each is arranged to some extent continuously, or arranged in a fixed order). . Therefore, the ET-ST-NBE copolymer of the present invention may be a random copolymer, an ABC block copolymer, or other ordered copolymer, but is preferably a random copolymer or ABC. A type block copolymer, more preferably a random copolymer.

  The ratio of each structural unit in the NBE-ET-ST copolymer of the present invention is arbitrary, but the content of ethylene structural units relative to all structural units is usually about 20 to 80 mol%. In the production of the NBE-ET-ST copolymer (described later), the ethylene structural unit content is determined by the ratio of norbornene to styrene, the pressure of ethylene, the amount of solvent, the reaction temperature, the type of catalyst (the central metal and the arrangement). It can be controlled by the type of ligand) and the type of promoter, and is not limited to the above range.

  Moreover, the ratio of the styrene structural unit and the norbornene structural unit in the NBE-ET-ST copolymer of the present invention is arbitrary. The ratio of both can be controlled by adjusting the ratio of styrene and norbornene as the monomer raw material in the production (described later) of the NBE-ET-ST copolymer.

The content rate of the ethylene structural unit and the ratio of the styrene structural unit and the norbornene structural unit in the NBE-ET-ST copolymer of the present invention can be measured by analyzing a ¹³ C-NMR spectrum. Specifically, since each peak of the ¹³ C-NMR spectrum of the NBE-ET-ST copolymer is attributed to each carbon as shown in FIG. 16, if the ratio is obtained based on the peak area. Good.
Specifically, the peak area P ₁₂₈ of 128ppm vicinity of the peak (ST4 carbon), the peak area P ₃₃ peak around 33ppm (NBE1 carbon), the peak area P of 30.5 near the peak (ET2 carbon + NBE2 carbon) It can be obtained from the ratio of _30.5 . That is, it can be determined according to the following equation.
Styrene content (%) = [ _P128 / ( _P128 + 2 × _P30.5 )] × 100,
Norbornene content (%) = [4 × P ₃₃ / (P ₁₂₈ + 2 × P _30.5 )] × 100,
Ethylene content (%) = [(2 × P _30.5 -4 × P ₃₃ ) / (P ₁₂₈ + 2 × P _30.5 )] × 100

The styrene structural unit in the NBE-ET-ST copolymer of the present invention is represented by the following formula (A). The substituent (R) _n on the phenyl ring in formula (A) may or may not be present (unsubstituted). When the structural units represented by formula (A) are continuously arranged, they are usually head-to-tail bonded. The styrene structural unit contained in the NBE-ET-ST copolymer of the present invention may be one type or two or more types.
R and n in the following formula (A) are the same as R and n described in formula (A) which is a repeating unit in the styrene (co) polymer.

The tacticity of the styrene structural unit of the NBE-ET-ST copolymer of the present invention is preferably high syndiotactic. Specifically, the NBE-ET-ST copolymer of the present invention, which is a random copolymer, has a syndiotactic dyad ratio in all two continuous units (dyads) of styrene structural units contained therein. Usually, it is 60 r% or more, preferably 80 r% or more, more preferably 98 r% or more.
The syndiotacticity of a chain composed of styrene structural units can be measured by the same method as the method for measuring syndiotacticity in the styrene-ethylene copolymer described above.

  As described above, the NBE-ET-ST copolymer of the present invention includes a norbornene structural unit. Here, the norbornene means a compound having a 2-norbornene skeleton represented by the following formula.

In the above formula, R ¹ and R ² are arbitrary and are not particularly limited. For example, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), or R ¹ and R ² may be combined to form an alkylene chain or an alkenylene chain. Specific examples of the norbornene include 2-norbornene, dicyclopentadiene, tetracyclododecane (TCD), 1,4-methanotetrahydrofluorene (MTF) and the like.
The norbornene is more preferably 2-norbornene or dicyclopentadiene in which R ¹ and R ² are hydrogen atoms.

The norbornene structural unit in the ET-ST-NBE copolymer of the present invention preferably has a high selectivity of the addition polymerization unit. That is, the structural unit of the polynorbornenes may be an addition polymerization unit and a ring-opening polymerization unit shown below, but the addition polymerization unit for all the structural units of the norbornenes in the NBE-ET-ST copolymer of the present invention. The ratio is high. Specifically, the ratio of the addition polymerization unit in all structural units of norbornenes in the NBE-ET-ST copolymer of the present invention is usually 95% or more, preferably about 100%. The ratio of the addition polymerization unit and the ring-opening polymerization unit can be determined from the ¹ H-NMR spectrum.

  Although the molecular weight distribution of the NBE-ET-ST copolymer of this invention is not specifically limited, Mw / Mn which is the parameter | index is 2.0 or less normally, Preferably it is 1.5 or less. The molecular weight distribution means a value (Mw / Mn) measured by the GPC method (measured at 145 ° C. using polystyrene as a standard substance and 1,2-dichlorobenzene as an eluent). For example, a GPC measuring device (TOSOH HLC 8121 GPC / HT).

The molecular weight of the NBE-ET-ST copolymer of the present invention is not particularly limited, but the number average molecular weight is usually 5 × 10 ⁵ or less. Although a minimum is not specifically limited, What is necessary is just 5000 or more.

  The NBE-ET-ST copolymer of the present invention usually has a glass transition temperature, and the temperature is not particularly limited, but is usually about 60 ° C. The glass transition temperature is measured by a differential scanning calorimetry (DSC) method.

7). Copolymer of dicyclopentadiene and ethylene of the present invention (DCPD-ET copolymer)
The copolymer of dicyclopentadiene and ethylene of the present invention is a copolymer containing a dicyclopentadiene structural unit and an ethylene structural unit. In the DCPD-ET copolymer of the present invention, the structural units may be arranged in an arbitrary order. That is, each structural unit may be arranged at random, or arranged with some regularity (for example, each arranged alternately, arranged to some extent continuously, arranged in a certain order) Yes) Therefore, the DCPD-ET copolymer of the present invention may be a random copolymer, an alternating copolymer, a block copolymer, or other ordered copolymer, preferably a random copolymer or A block copolymer, more preferably a random copolymer.

The content of the dicyclopentadiene structural unit with respect to all the structural units contained in the DCPD-ET copolymer of the present invention is not particularly limited, but is usually 10 mol% or more, preferably 20 mol%, preferably 30 mol% or more. It is more preferable. Moreover, although an upper limit is not specifically limited, Usually, it is 60 mol% or less, Preferably it is 50 mol% or less, More preferably, it is 40 mol% or less.
The content can be measured by analyzing a ¹ H-NMR spectrum. Specifically, each peak in the ¹ H-NMR spectrum of the DCPD-ET copolymer is attributed to each carbon of the copolymer, as shown in FIG. 19, and thus is determined from the ratio of these peak areas. be able to. Specifically, it is possible to find eg 3ppm vicinity of the peak (DCPD1 hydrogen) peak area P _3, the ratio of the peak area P _0.7-1.7 peaks 0.7~1.7ppm (DCPD4 hydrogen + ET4 hydrogen). That is, it can be determined based on the following formula.
DCPD (%) = [4P ₃ / (P _0.7-1.7 )] × 100
The content can be controlled by adjusting the amount (or concentration) of dicyclopentadiene in the raw material for the production (described later) of the DCPD-ET copolymer.

Dicyclopentadiene has a C═C double bond derived from a norbornene structure and a C═C double bond derived from a cyclopentene structure. The ratio of the dicyclopentadiene structural unit based on the C═C double bond derived from the norbornene structure to the total structural unit of the dicyclopentadiene in the DCPD-ET copolymer of the present invention is usually 80% or more, preferably 90 % Or more, more preferably 95% or more, and further preferably 99% or more.
Similarly to the norbornene structural unit, the dicyclopentadiene structural unit based on the C═C double bond derived from the norbornene structure can be an addition polymerization unit and a ring-opening polymerization unit represented by the following formula. The ratio of the addition polymerization unit to the total structural unit of dicyclopentadiene in the -ET copolymer is usually 80% or more, preferably 90% or more, more preferably 95% or more, and further preferably 99% or more.
The content can be determined from ¹ H-NMR spectrum data.

  The molecular weight distribution of the DCPD-ET copolymer of the present invention is not particularly limited, but the index Mw / Mn is usually 3 or less, preferably 2 or less. The molecular weight distribution means a value (Mw / Mn) measured by the GPC method (measured at 145 ° C. using polystyrene as a standard substance and 1,2-dichlorobenzene as an eluent). For example, a GPC measuring device (TOSOH HLC 8121 GPC / HT).

The molecular weight of the DCPD-ET copolymer of the present invention is not particularly limited, but the number average molecular weight is usually 100,000 or more, preferably 200,000 or more, more preferably 300,000 or more, and further preferably 400,000 or more.
Although an upper limit is not specifically limited, A number average molecular weight should just be 1 million or less.

  The DCPD-ET copolymer of the present invention usually has a glass transition temperature, and the temperature is not particularly limited, but is usually about 160 to 200 ° C. The glass transition temperature is measured by a differential scanning calorimetry (DSC) method.

<Method for producing polymer compound of the present invention>
The method for producing a polymer compound of the present invention is characterized in that an arbitrary polymerizable monomer is polymerized (addition polymerization) using the above-described polymerization catalyst composition of the present invention.
The production method of the present invention may be the same as the conventional method of producing a polymer compound by an addition polymerization reaction using a coordination ion polymerization catalyst, except that the catalyst composition of the present invention is used as a polymerization catalyst. it can.

Specifically, for example, the following procedure can be used.
1. Polymerization is performed by supplying a polymerizable monomer into a system (preferably a liquid phase) containing the catalyst composition of the present invention. Here, if the monomer is liquid, it can be supplied by dropping, and if it is gas, it can be supplied through a gas pipe (for example, bubbling if it is a liquid phase reaction system).
2. Polymerization is carried out by adding the catalyst composition of the present invention or separately adding the components of the catalyst composition to a system (preferably a liquid phase) containing a polymerizable monomer. The catalyst composition to be added may be prepared in advance (preferably prepared in a liquid phase) and activated (in this case, it is preferable to add the catalyst composition so as not to touch outside air).

Here, the polymerizable monomer is a monomer having addition polymerization, for example, an olefin monomer, an epoxy monomer, an isocyanate monomer, a lactone monomer, a lactide polymer, a cyclic carbonate monomer, an alkyne monomer, and the like. A combination of these may also be used.
Of these, preferably one or more olefinic monomers, more preferably substituted and unsubstituted styrene, ethylene, α-olefin (including 1-hexene), diene, cyclic olefin (norbornenes and the like) 1 or 2 or more types of monomers selected from (including cyclohexadiene). Here, as the diene which is an olefinic monomer, 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,4 -Cyclic dienes such as dimethyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 2,4-hexadiene and cyclohexadiene can be exemplified.

The production method may be any method such as a gas phase polymerization method, a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a solid phase polymerization method. In the case of the solution polymerization method, the solvent to be used is not particularly limited as long as it is inactive in the polymerization reaction and can dissolve the monomer and the catalyst. For example, saturated aliphatic hydrocarbons such as butane, pentane, hexane and heptane; saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; methylene chloride, chloroform, carbon tetrachloride and trichloro Halogenated hydrocarbons such as ethylene, perchlorethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chlorotoluene; ethers such as tetrahydrofuran and diethyl ether.
Moreover, the solvent which does not have toxicity with respect to a biological body is preferable. Specifically, an aromatic hydrocarbon, particularly toluene is preferable. The solvent may be used alone or in combination of two or more.
The amount of the solvent used is arbitrary, but is preferably an amount that makes the concentration of the complex contained in the polymerization catalyst 0.1 to 0.0001 mol / l.

The polymerization temperature when the polymerization of the present invention is performed by solution polymerization can be performed at any temperature, for example, in the range of -90 to 100 ° C. Although it may be appropriately selected according to the type of monomer to be polymerized, etc., it can usually be performed at around room temperature, that is, at about 25 ° C.
The polymerization time is about several seconds to several hours, and may be appropriately selected according to the type of monomer to be polymerized. Usually, it may be 1 hour or less, and in some cases 1 minute or less.
However, these reaction conditions can be appropriately selected according to the polymerization reaction temperature, the type and molar amount of the monomer, the type and amount of the catalyst composition, etc., and should be limited to the ranges exemplified above. There is no.

For the production of the copolymer,
1) If it is a random copolymer or an alternating copolymer, it can be produced by polymerizing a mixture of two or more monomers in the presence of a catalyst composition,
2) If it is a block copolymer, it can manufacture by supplying each monomer in order in the reaction system containing a catalyst composition.

Examples of the polymer compound produced by the production method of the present invention include the following, but are not limited thereto.
1) A substituted or unsubstituted styrene polymer, or a copolymer of substituted or unsubstituted styrene and substituted styrene.
2) A copolymer of substituted or unsubstituted styrene and ethylene.
3) Ethylene polymer.
4) α-olefin (including 1-hexene) polymer.
5) Copolymer of ethylene and α-olefin (including 1-hexene).
6) Copolymer of ethylene and norbornene.
7) 1,3-cyclohexadiene polymer.
8) A copolymer of 1,3-cyclohexadiene and substituted or unsubstituted styrene.
9) A copolymer of 1,3-cyclohexadiene and ethylene.
9) Norbornenes, copolymers of substituted or unsubstituted styrene and ethylene.
10) A copolymer of dicyclopentadiene and ethylene.
11) Diene polymer or copolymer.
12) Copolymer of substituted or unsubstituted styrene and conjugated diene.
In addition, the manufacturing method of the (co) polymer of said 1) -2), 7) -10), and 12) is demonstrated in detail below.

1. Method for Producing Styrene Polymer or Copolymer Styrene polymer or copolymer is obtained by polymerizing substituted or unsubstituted styrene or a mixture thereof (hereinafter also simply referred to as “styrene compound”) using the catalyst composition of the present invention. Can be manufactured.
As the complex in the catalyst composition, a complex in which the central metal is scandium Sc, yttrium Y, gadolinium Gd, lutetium Lu, more preferably scandium Sc is used. On the other hand, the ionic compound in the catalyst composition is preferably a compound composed of a tetravalent boron anion and a carbonium cation such as [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]. It is preferable that the complex and the ionic compound have a molar ratio of about 1: 1.

As a specific procedure, for example, in the solvent (preferably toluene), the catalyst composition of the present invention is constituted to produce active species, and further, the styrene compound is supplied while stirring this. The reaction temperature is preferably adjusted to about 25 ° C.
The amount of the solvent used in the polymerization reaction is preferably about 5 ml per 1 ml of styrene monomer, but is not particularly limited thereto.
The amount of the styrene compound provided is preferably 100 to 3000 times in molar ratio to the complex, and preferably 500 to 2500 times when using the Sc complex. When the ratio is increased, a polystyrene (co) polymer having a large molecular weight can be produced. However, when the ratio is significantly greater than 3000 times, syndiotacticity may be slightly decreased.
The polymerization reaction is often completed in about several seconds to 1 hour. In particular, when using an Sc complex, the process is often completed within 1 minute. When the reaction is completed, the viscosity of the reaction system increases and stirring may not be possible.

After completion of the reaction, the produced polymer can be precipitated by placing the reaction mixture in methanol or the like. The precipitated polymer is collected by filtration and dried to obtain a styrene (co) polymer. The yield of the styrene (co) polymer obtained varies depending on the type of complex used, but can be approximately 100%. In particular, high yields are often obtained when Sc complexes are used.
The styrene (co) polymer produced in this way can have a high syndiotacticity. In a particularly preferred embodiment, the styrene (co) polymer of the present invention described above can be produced.

2. Production method of ethylene-styrene copolymer The ethylene-styrene copolymer can be produced by polymerizing ethylene and one or more styrene compounds using the catalyst composition of the present invention. The complex, ionic compound, and relative ratio thereof in the catalyst composition are preferably the same as those in the method for producing the styrene polymer or copolymer.

As a specific procedure, for example, ethylene gas is continuously supplied into a solution (preferably a toluene solution) containing a styrene compound. To this is added the catalyst composition of the present invention. The reaction temperature is preferably adjusted to about 25 ° C.
The amount of the solvent used in the polymerization reaction is preferably about 50 ml with respect to 1 ml of styrene, but is not particularly limited thereto.
The amount of the styrene compound may be about 100 to 3000 times in molar ratio with respect to the complex (or ionic compound). If the amount of the styrene compound is increased, the molecular weight of the resulting copolymer can be increased, and the styrene content can be increased.
Although the pressure of the supplied ethylene gas can be adjusted arbitrarily, it may be usually 1 atm. It is considered that the molecular weight of the copolymer or the ethylene content can be adjusted by adjusting the pressure.
The catalyst composition is preferably added as a solution (preferably a solution containing active species) obtained by reacting a complex and an ionic compound in a solvent (preferably toluene) in advance.
The reaction time is preferably about several seconds to 1 hour, particularly about several minutes when an Sc complex is used.

After completion of the reaction, the produced polymer can be precipitated by placing the reaction mixture in methanol or the like. The precipitated polymer is collected by filtration and dried to obtain a styrene-ethylene copolymer.
The ethylene-styrene copolymer thus produced is a random copolymer and may have a high syndiotacticity. In preferred embodiments, it may have a sharp molecular weight distribution.

On the other hand, after the catalyst composition of the present invention is added and polymerized in a solution containing styrene compound (preferably toluene solution), the styrene compound in the system disappears (can disappear in a few minutes), and then ethylene gas Is supplied, an ethylene-styrene copolymer of a block copolymer is obtained. In addition, after polymerizing ethylene, styrene may be supplied and polymerized.
The block copolymer ethylene-styrene copolymer thus obtained can have a high syndiotacticity in the styrene block chain and a sharp molecular weight distribution.

3. Method for Producing 1,3-Cyclohexadiene Polymer A 1,3-cyclohexadiene polymer can be produced by polymerizing 1,3-cyclohexadiene using the catalyst composition of the present invention. As the complex in the catalyst composition, a complex in which the central metal is scandium Sc, yttrium Y, lutetium Lu, dysprosium Dy, holmium Ho, erbium Er, more preferably scandium Sc is used. From the viewpoint of the yield of the resulting polymer, the central metal is preferably Sc. On the other hand, examples of the ionic compound in the catalyst composition include tetravalent boron anions and carbonium cations such as [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ], or [Ph (Me) ₂ NH] [ A compound comprising a tetravalent boron anion and an anilinium cation such as B (C ₆ F ₅ ) ₄ ] is preferred. It is preferable that the complex and the ionic compound have a molar ratio of about 1: 1.

As a specific procedure, for example, an active species is produced by constituting the catalyst composition of the present invention in a solvent (preferably toluene). While stirring the resulting solution, 1,3-cyclohexadiene is fed to this solution. The reaction temperature is preferably adjusted to about 25 ° C.
The amount of the solvent used in the polymerization reaction is preferably about 5 ml with respect to 10 mmol of 1,3-cyclohexadiene, but is not particularly limited thereto.
The amount of 1,3-cyclohexadiene to be supplied is preferably 100 to 3000 times in molar ratio to the complex. When the ratio is increased, a polystyrene (co) polymer having a large molecular weight can be produced. However, when the ratio is too large, cis-syndiotacticity may decrease.
The polymerization reaction is usually completed in about several hours.

After completion of the reaction, the produced polymer can be precipitated by placing the reaction mixture in methanol or the like. The precipitated polymer is collected by filtration and dried to obtain a 1,3-cyclohexadiene polymer. The yield of the resulting 1,3-cyclohexadiene polymer varies depending on the type of complex used, but can be around 50%.
The 1,3-cyclohexadiene polymer produced in this way has a high 1,4-selectivity and can have a high cis-syndiotacticity. In a particularly preferred embodiment, the aforementioned 1,3-cyclohexadiene polymer of the present invention can be produced.

4. Method for producing copolymer of 1,3-cyclohexadiene and styrene The copolymer of 1,3-cyclohexadiene and styrene is obtained by converting 1,3-cyclohexadiene and substituted or unsubstituted styrene into the catalyst of the present invention. It can manufacture by making it copolymerize using a composition. The complex, ionic compound, relative ratio, etc. in the catalyst composition are preferably the same as those in the method for producing a 1,3-cyclohexadiene polymer.

  As a specific procedure, for example, in the solvent (preferably toluene), the catalyst composition of the present invention is constituted to produce active species, and while stirring this, 1,3-cyclohexadiene and styrene are further added. Supply. 1,3-cyclohexadiene and styrene may be supplied in a state dissolved in a solvent (for example, toluene). Further, a random copolymer can be obtained by polymerizing by supplying 1,3-cyclohexadiene and styrene as a mixture, and after polymerizing by supplying one of 1,3-cyclohexadiene or styrene, A block copolymer can be obtained by supplying another one for polymerization (living copolymerization).

The reaction temperature is preferably adjusted to about 25 ° C.
The amount of the solvent used in the polymerization reaction is preferably about 5 to 10 ml with respect to a total mole of 20 mmol of 1,3-cyclohexadiene and styrene, but is not particularly limited thereto.
The amount of 1,3-cyclohexadiene and styrene provided is preferably 100 to 3000 times, more preferably 100 to 1000 times in terms of molar ratio to the complex. When the ratio is increased, a polymer having a large molecular weight can be produced. However, when the ratio is too large, the tacticity of 1,3-cyclohexadiene or styrene structural units may be decreased.
The polymerization reaction is usually completed in about several hours.

After completion of the reaction, the produced polymer can be precipitated by placing the reaction mixture in methanol or the like. The precipitated polymer is collected by filtration and dried to obtain a 1,3-cyclohexadiene-styrene copolymer.
The copolymer of 1,3-cyclohexadiene and styrene thus produced has a high ratio of 1,4-structural units to all structural units of 1,3-cyclohexadiene, and is highly cis-syndiotactic. possible. Moreover, a styrene structural unit may have a high syndiotacticity. In a preferred embodiment, the above-described CHD-ST copolymer of the present invention is produced.

5. Method for producing copolymer of 1,3-cyclohexadiene and ethylene The copolymer of 1,3-cyclohexadiene and ethylene is obtained by using 1,3-cyclohexadiene and ethylene by using the catalyst composition of the present invention. It can be produced by copolymerization. The complex, ionic compound, relative ratio, etc. in the catalyst composition are preferably the same as those in the method for producing a 1,3-cyclohexadiene polymer.

As a specific procedure, for example, ethylene gas is continuously supplied into a solution (preferably a toluene solution) containing 1,3-cyclohexadiene. A random copolymer can be obtained by adding the catalyst composition of this invention to this.
The block copolymer is obtained, for example, by adding the catalyst composition of the present invention to a solution containing 1,3-cyclohexadiene to polymerize 1,3-cyclohexadiene, and further supplying ethylene gas for polymerization. It is done.

The amount of the solvent used in the polymerization reaction may be about 20 to 40 ml with respect to 1.0 g of 1,3-cyclohexadiene, but is not particularly limited thereto.
The amount of 1,3-cyclohexadiene may be about 100 to 3000 times in molar ratio to the complex (or ionic compound). When the amount of 1,3-cyclohexadiene is increased, the molecular weight of the resulting copolymer tends to decrease, and the 1,3-cyclohexadiene content tends to increase.
The reaction temperature may be adjusted to about 25 ° C., but the molecular weight of the resulting copolymer can be increased by raising the reaction temperature.
Although the pressure of the supplied ethylene gas can be adjusted arbitrarily, it may be usually 1 atm. It is considered that the molecular weight of the copolymer or the ethylene content can be adjusted by adjusting the pressure.
The catalyst composition is preferably added as a solution (preferably a solution containing active species) obtained by reacting a complex and an ionic compound in a solvent (preferably toluene) in advance.
The polymerization reaction is usually completed in about several hours.

  After completion of the reaction, the produced copolymer can be precipitated by opening the reaction mixture in methanol or the like. The precipitated polymer is collected by filtration and dried to obtain a 1,3-cyclohexadiene-ethylene copolymer. In a particularly preferred embodiment, the above-described CHD-ET copolymer of the present invention can be produced.

6). Process for Producing Copolymer of Ethylene, Substituted or Unsubstituted Styrene and Norbornenes Copolymer of ethylene, substituted or unsubstituted styrene and norbornene is a catalyst composition of the present invention comprising ethylene and substituted or unsubstituted styrene and norbornene. It can manufacture by making it copolymerize using a thing. The complex, ionic compound, relative ratio, etc. in the catalyst composition are preferably the same as those in the method for producing a 1,3-cyclohexadiene polymer.
The norbornenes are the same as the norbornenes described in the above-described NBE-ET-ST copolymer of the present invention.

As a specific procedure, for example, ethylene gas is continuously supplied into a solution (preferably a toluene solution) containing norbornenes and substituted or unsubstituted styrene. A random copolymer can be obtained by adding the catalyst composition of this invention to this.
Further, the ABC type block copolymer is polymerized by adding the catalyst composition of the present invention to a solution containing, for example, either norbornenes or styrene, and then polymerizing another one, and then ethylene gas. It can be obtained by supplying.

The amount of the solvent used in the polymerization reaction may be about 40 ml with respect to 20.0 mmol of norbornenes, but is not particularly limited thereto.
The amount of norbornene used can be about 100 to 3000 times in molar ratio to the complex (or ionic compound), but is not particularly limited.
The amount of styrene used may be adjusted according to the content of the styrene structural unit of the target copolymer (if the content of the styrene structural unit in the target copolymer is high, the amount of styrene can be increased. Just fine).
The pressure of the ethylene gas to be supplied can be arbitrarily adjusted, but normally it may be 1 atm. It is considered that the molecular weight of the copolymer or the ethylene content can be adjusted by adjusting the pressure.
The reaction temperature is preferably adjusted to about 25 ° C., but the molecular weight of the copolymer obtained can be increased by raising the reaction temperature.
The catalyst composition is preferably added as a solution (preferably a solution containing active species) obtained by reacting a complex and an ionic compound in a solvent (preferably toluene) in advance.
The polymerization reaction is usually completed in about several minutes.

  After completion of the reaction, the produced copolymer can be precipitated by adding methanol to the reaction mixture. The precipitated polymer is collected by filtration and dried to obtain a copolymer of ethylene, substituted or unsubstituted styrene and norbornenes. In a particularly preferred embodiment, the above-described NBE-ST-ET copolymer of the present invention is produced.

7). Method for Producing Dicyclopentadiene and Ethylene Copolymer A dicyclopentadiene and ethylene copolymer can be produced by copolymerizing dicyclopentadiene and ethylene using the catalyst composition of the present invention. The complex, ionic compound, relative ratio, etc. in the catalyst composition are preferably the same as those in the method for producing a 1,3-cyclohexadiene polymer.

As a specific procedure, for example, ethylene gas is continuously supplied into a solution containing dicyclopentadiene (preferably a toluene solution). A random copolymer can be obtained by adding the catalyst composition of the present invention thereto.
In addition, after adding the catalyst composition of the present invention to a solution containing dicyclopentadiene to polymerize dicyclopentadiene, an ethylene gas is supplied to perform polymerization (block copolymerization) to obtain a block copolymer. it can.

The amount of the solvent used in the polymerization reaction may be about 40 ml with respect to 20.0 mmol of dicyclopentadiene, but is not particularly limited thereto.
The amount of dicyclopentadiene used may be about 100 to 3000 times in molar ratio to the complex (or ionic compound). Needless to say, if the amount of dicyclopentadiene is increased, the content of the dicyclopentadiene structural unit in the resulting copolymer is increased.
Although the pressure of the supplied ethylene gas can be adjusted arbitrarily, it may be usually 1 atm. It is considered that the molecular weight of the copolymer or the ethylene content can be adjusted by adjusting the pressure.
The catalyst composition is preferably added as a solution (preferably a solution containing active species) obtained by reacting a complex and an ionic compound in a solvent (preferably toluene) in advance.
The polymerization reaction is usually completed in about several minutes.

  After completion of the reaction, the produced copolymer can be precipitated by adding methanol or the like to the reaction mixture. The precipitated polymer is collected by filtration and dried to obtain a copolymer of dicyclopentadiene and ethylene. In a particularly preferred embodiment, the above-described DCPD-ET copolymer of the present invention can be produced.

8). Process for producing conjugated diene-styrene copolymer A conjugated diene-styrene copolymer is obtained by polymerizing one or two or more conjugated dienes and one or two or more styrene compounds using the catalyst composition of the present invention. Can be manufactured. The complex, ionic compound, relative ratio, etc. in the catalyst composition are preferably the same as those in the method for producing a styrene polymer or copolymer.

Although the example of a concrete procedure is shown below, it is not specifically limited to this.
A solution containing the catalyst composition of the present invention is prepared. The solvent of the solution is toluene or the like. A mixture obtained by adding a styrene compound and a conjugated diene to the prepared solution is stirred to cause a polymerization reaction. The amount of the solvent used in the polymerization reaction is preferably 1 to 10 ml with respect to 1 ml of the monomer mixture. The amount of the styrene compound may be about 100 to 2000 times in molar ratio with respect to the complex (or ionic compound).
The ratio of styrene compound to conjugated diene (styrene / conjugated diene) is arbitrary, but can be 0.5 to 8 in terms of molar ratio. By adjusting the ratio of the styrene compound and the conjugated diene, the content ratio of the styrene structural unit and the conjugated diene structural unit in the obtained copolymer can be adjusted.
The reaction temperature is preferably adjusted to about 25 ° C. The reaction time varies depending on the amount ratio of the styrene compound to be polymerized and the conjugated diene compound, but is preferably about 1 to 5 hours. If the reaction time is extended, the styrene content of the resulting copolymer may increase.

  After completion of the reaction, the polymerization reaction is stopped by adding methanol to the reaction mixture, and the resulting polymer can be precipitated by pouring it into methanol. The precipitated polymer is collected by filtration and dried to obtain a conjugated diene-styrene copolymer.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail with reference to an Example and a reference example, the range of this invention is not limited by these. ¹³ C-NMR was measured at a frequency of 75.5 MHz.

<Reference example>
<Synthesis of metallocene complexes>
The compounds were synthesized according to the methods described in the following documents (1) and (2).
(1) Tardif, O .; Nishiura, M .; Hou, ZM Organometallics 22, 1171, (2003).
(2) Hultzsch, KC; Spaniol, TP; Okuda, J. Angew. Chem. Int. Ed, 38, 227, (1999).

1. Synthesis of (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF)
In THF, ScCl ₃ and LiCH ₂ SiMe ₃ were reacted at a ratio of 1: 3, and from the obtained reaction product, a hexane solution (10 ml) of Sc (CH ₂ SiMe ₃ ) ₃ (1.366 g, 3.03 mmol) was added. Prepared. C ₅ Me ₄ H (SiMe ₃ ) (0.589 g, 3.03 mmol) was added to this preparation at room temperature. The resulting pale yellow solution was stirred at room temperature for 2 hours.
After stirring, the mixture was concentrated under reduced pressure, and the resulting residual oil was cooled overnight (−30 ° C.), and (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (1.145 g, 2.36 mmol, 78% yield) was obtained as colorless cubic crystals.

The physical property data of (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) are shown below.
¹ H NMR (C ₆ D ₆ , 22 ° C): δ (ppm) -0.30 (d, 2 H, CH ₂ SiMe ₃ , J _HH = 11.5 Hz), -0.25 (d, 2 H, CH ₂ SiMe ₃ , J _HH = 11.5 Hz) 0.29 (s, 18 H, CH ₂ SiMe ₃ ), 0.43 (s, 9 H, C ₅ Me ₄ SiMe ₃ ), 1.19 (m, 4 H, THF-b-CH ₂ ), 1.91 (s, 6 H, C ₅ Me ₄ ), 2.22 (s, 6 H, C ₅ Me ₄ ), 3.63 (m, 4 H, THF-a-CH ₂ ).
¹³ C NMR (C ₆ D ₆ , 22 ° C): δ (ppm) 2.83 (s, 3 C, C ₅ Me ₄ SiMe ₃ ), 4.62 (s, 6 C, CH ₂ SiMe ₃ ), 12.12 (s, 2 C, C ₅ Me ₄ ), 15.43 (s, 2 C, C ₅ Me ₄ ), 24.93 (s, 2 C, THF), 40.41 (s, 1 C, CH ₂ SiMe ₃ ), 71.51 (s, 2 C, THF), 116.64 (s, 1 C, ipso-C ₅ (SiMe ₃ ) Me ₄ , 124.15 (s, 2 C, C ₅ Me ₄ ), 127.96 (s, 2 C, C ₅ Me ₄ ).
IR (nujol): 628 (s), 672 (s), 713 (s), 755 (s), 819 (s), 851 (s), 889 (s), 1013 (s), 1038 (m), 1131 (m), 1175 (w), 1238 (s), 1247 (s), 1280 (w), 1328 (s), 1344 (m), 1407 (w).
Anal.Calcd for C ₂₄ H ₅₁ OScSi ₃ : C, 59.45; H, 10.60. Found: C, 58.54; H, 10.41.

2. Synthesis of (C ₅ Me ₄ SiMe ₃ ) Ln (CH ₂ SiMe ₃ ) ₂ (THF) (Ln = Y, Gd, Ho, Lu) (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ Synthesized in the same manner as (THF).

3. Synthesis of (C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂
Pentamethylcyclopentadiene (409 mg, 3 mmol) was added to a THF solution (10 ml) of Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₃ (1.323 g, 3 mmol). The solution was stirred at 70 ° C. for 12 hours and then concentrated under reduced pressure to obtain a yellow powder. The resulting yellow powder was washed with hexane and recrystallized from benzene to yield (C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ (538 mg, 40% yield) in yellow Obtained as crystals.

Physical property data of (C ₅ Me ₅ ) Sc (CH ₂ C ₆ H ₄ NMe ₂ -o) ₂ is shown below.
¹ H NMR (C ₆ D ₆ , 60 ° C): δ (ppm) 7.13 (d, J = 7.3 Hz, 2H, aryl), 6.99 (t, J = 7.4 Hz, 2H, aryl), 6.71-6.83 ( m, 4H, aryl), 2.35 (s, 12H, NMe ₂ ), 1.73 (s, 15H, C ₅ Me ₅ ), 1.47 (s, 4H, CH ₂ ).
¹³ C NMR (C ₆ D ₆ , 60 ° C): δ (ppm) 11.8 (CpMe), 45.5 (br NMe ₂ ), 47.3 (CH ₂ ), 117.1, 119.6, 120.9, 126.5, 130.7, 145.7, 147.7 ( aromatic and Cp ring carbons).
Anal.Calcd.for C ₂₈ H ₃₉ ScN ₂ : C 74.97; H 8.76; N 6.24. Found: C 74.89; H 8.67; N 6.19.

<Example 1> Production of styrene polymer
In a 100 ml glass reaction vessel, a toluene solution (5 ml) of (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (10 mg, 21 μmol), [Ph ₃ C] [B ( C ₆ F ₅ ) ₄ ] (19 mg, 21 μmol) in toluene (7 ml) was added continuously. After 1 minute, styrene (2.148 g, 21 mmol) was added with vigorous stirring (stirring with a magnetic steerer). Within a few seconds, the viscosity of the solution increased and stirring was stopped. The reaction mixture was poured into methanol (400 ml) to precipitate the polymer. The white powder polymer was collected by filtration and dried at 60 ° C. under reduced pressure to obtain 2.14 g (constant weight) of polymer (100%).

<Examples 2-9> Production of styrene polymer (1) Example 2: Polystyrene was obtained in the same manner as in Example 1, except that the amount of styrene was 10.5 mmol.
(2) Example 3: Polystyrene was obtained in the same manner as in Example 1, except that the amount of styrene was 14.7 mmol.
(3) Example 4: Polystyrene was obtained in the same manner as in Example 1, except that the amount of styrene was 31.5 mmol.
(4) Example 5: Polystyrene was obtained in the same manner as in Example 1 except that the amount of styrene was 42.0 mmol.
(5) Example 6: Polystyrene was obtained in the same manner as in Example 1, except that the amount of styrene was 52.5 mmol and the reaction time was 1 minute.
(6) Example 7: In Example 1, the complex was (C ₅ Me ₄ SiMe ₃ ) Y (CH ₂ SiMe ₃ ) ₂ (THF) (21 μmol), the amount of styrene was 2.1 mmol, and the reaction time was Polystyrene was obtained in the same manner except that the time was 30 minutes.
(7) Example 8: Polystyrene was obtained in the same manner as in Example 7, except that the complex was changed to (C ₅ Me ₄ SiMe ₃ ) Gd (CH ₂ SiMe ₃ ) ₂ (THF) (21 μmol). .
(8) Example 9: Polystyrene was obtained in the same manner as in Example 7, except that the complex was changed to (C ₅ Me ₄ SiMe ₃ ) Lu (CH ₂ SiMe ₃ ) ₂ (THF) (21 μmol). .
(9) Example 10: In a 100 ml flask, a toluene solution (50 ml) of (C5Me5) Sc (CH2C6H4NMe2-o) 2 (11 mg, 0.025 mmol), [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (23 mg, 0.025 mmol) in toluene (7 ml) was added continuously. After 10 minutes, styrene (10.415 g, 100 mmol) was added to the resulting solution with vigorous stirring. In a few minutes, the viscosity of the reaction solution increased and stirring was stopped.
The reaction mixture was poured into methanol (400 ml) to precipitate a white powder polymer. The precipitate collected by filtration was dried at 60 ° C. under reduced pressure to obtain a polymer (10.42 g, 100%).

(10) Comparative Example 1: In the same manner as in Example 1, except that the complex was changed to (C ₅ Me ₄ SiMe ₂ CH ₂ PPh ₂ ) Y (CH ₂ SiMe ₃ ) ₂ (THF) (21 μmol). Although an experiment was conducted, polystyrene was not obtained.

  The production methods of Examples 1 to 10 and the physical properties of the obtained styrene polymers are summarized in Table 1.

In Table 1 above,
1. The yield was calculated by (mass of styrene polymer obtained) / (mass of styrene monomer used).
2. The activity is expressed in kg of polymer produced when the reaction is carried out for 1 hour using 1 mol of the complex.
3. The content of syndiotactic polystyrene was calculated by “(weight of polymer insoluble in refluxed 2-butanone) / (weight of all polymers obtained)”.
The syndiotacticity was 99% or more in terms of pentad (rrrr) according to NMR spectrum data. (NMR measurement solvent was 1,2-dichlorobenzene-d ₄ and measurement temperature was 130 ° C.)
4). The number average molecular weight and molecular weight distribution were determined by GPC method (measured at 145 ° C. using polystyrene as a standard and 1,2-dichlorobenzene as an eluent).
5. The melting point was measured by DSC method.

As shown in Table 1 above, the syndiotacticity of the styrene polymers obtained in Examples 1 to 10 was 100%. In addition, Mw / Mn, which is an index of molecular weight distribution of the obtained styrene polymer, was 1.55 or less, indicating that the distribution was narrow.
Furthermore, it was found that the molecular weight can be adjusted by adjusting the ratio of the styrene monomer and the complex.

As described above, the syndiotacticity (pentad) of the styrene polymer of the present invention can be determined from a ¹³ C-NMR spectrum. Specifically, it can be determined by the integration ratio of the peak attributed to the aromatic C1 carbon or the peak attributed to the polystyrene main chain carbon.
For example, FIG. 1 is a ¹³ C-NMR spectrum chart of the styrene polymer obtained in Example 1, and the peak of c (about 145 ppm) attributed to the aromatic C1 carbon of racemic pentad is very sharp. It can be seen that it has a syndiotacticity of approximately 100 rrrr%. Furthermore, it can be seen that the a and b peaks attributed to the polystyrene main chain carbon of racemic pentad are also very sharp and have a syndiotacticity of approximately 100 rrrr%.

<Example 11> Production of ethylene-styrene copolymer, etc. In a glove box, toluene (35 ml) and styrene (2.148 g, 21 mmol) were placed in a 250 ml two-necked glass reaction vessel provided with a stirring rod. Was added. The glass reaction vessel was removed from the glove box and connected to a Schlenk line. The temperature of the reaction vessel was maintained at 25 ° C. using a water bath.
While rapidly stirring the mixture in the reaction vessel, ethylene gas (1 atm) was continuously fed into the reaction vessel.
On the other hand, (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (10 mg, 21 μmol) and [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (19 mg, 21 μmol) Reaction was carried out in a toluene solution (15 ml) to generate a predetermined amount of active species in the system. This was quickly added to the reaction vessel with a syringe to initiate polymerization.
After 2 minutes, methanol was added to terminate the polymerization reaction, and the reaction mixture was poured into methanol (400 ml) to precipitate the polymer. The precipitated polymer was collected by filtration and dried at 60 ° C. under reduced pressure to obtain 0.79 g (constant weight) of polymer.

<Examples 12 to 16> Production of ethylene-styrene copolymer (random) (1) Example 12: In Example 11, ethylene-styrene copolymer was prepared in the same manner except that the amount of styrene was 10 mmol. A polymer was obtained.
(2) Example 13: An ethylene-styrene copolymer was obtained in the same manner as in Example 11 except that the amount of styrene was 31 mmol.
(3) Example 14: In Example 11, the ethylene-styrene copolymer was obtained by the same method except having made the amount of styrene into 41 mmol.
(4) Example 15: A styrene copolymer was obtained in the same manner as in Example 11 except that the supply of ethylene was stopped.
(5) Example 16: An ethylene copolymer was obtained in the same manner as in Example 11 except that the amount of styrene was 0 mmol.

  The production methods of the polymers of Examples 11 to 16 and the physical properties of the polymers are summarized in Table 2.

In Table 2 above,
1. The activity is expressed in kg of polymer produced when the reaction is carried out for 1 hour using 1 mol of the complex.
2. The polystyrene content was determined from ¹³ C-NMR spectral data (measurement solvent was 1,2-dichlorobenzene-d ₄ and measurement temperature was 130 ° C.).
3. The number average molecular weight and molecular weight distribution (Mw / Mn) were calculated by the GPC method (measured at 145 ° C. using polystyrene as a standard and 1,2-dichlorobenzene as an eluent).
4). The melting point was measured by DSC method.

As described above, the syndiotacticity (dyad r%) of the ethylene-styrene copolymer of the present invention can be determined from a ¹³ C-NMR spectrum.
The spectrum chart of ¹³ C-NMR of the ethylene-styrene copolymers of Examples 11 to 14 is shown in FIG. 2 and a part of FIG. 2 (about 24 to 48 ppm) enlarged is shown in FIG.
Since all peaks observed at about 145.6 to 146.2 ppm are attributed to racemic dyad (r), it can be seen that the syndiotacticity is close to 100%.

<Example 17> Production of ethylene-styrene copolymer (block), etc. In a glove box, toluene (35 ml) and styrene (2.148 g, 21 mmol) were added to a 100 ml two-necked flask equipped with a stirring bar. Stir. The flask was removed from the glove box and connected to a Schlenk line. The temperature of the flask was maintained at 25 ° C. using a water bath, and argon gas was supplied.
On the other hand, (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (10 mg, 21 μmol) and [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (19 mg, 21 μmol) Reaction was carried out in a toluene solution (15 ml) to generate a predetermined amount of active species in the system. This was quickly added to the reaction vessel with a syringe to initiate polymerization.
Two minutes after the start of polymerization, ethylene gas (1 atm) was fed for 1 minute.
Thereafter, methanol (2 ml) was added to stop the polymerization reaction, and the reaction mixture was poured into methanol (400 ml) to precipitate the polymer. The precipitated polymer was collected by filtration and dried at 60 ° C. under reduced pressure to obtain 1.092 g (constant weight) of a white polymer. The physical properties of the obtained polymer are shown below.
Number average molecular weight: 1.12 × 10 ⁵
Molecular weight distribution (Mw / Mn): 1.23
Styrene content: 82%

In Example 17, when the reaction was stopped before ethylene gas was supplied (ethylene gas was not supplied), a 0.5 g (constant weight) polymer (styrene homopolymer) was obtained. The physical properties of this polymer are shown below.
Number average molecular weight: 0.60 × 10 ⁵
Molecular weight distribution (Mw / Mn): 1.23

Example 18 Production of Isoprene-Styrene Copolymer In a 100 ml flask in a glove box, (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (10 mg, 21 μmol) and [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (19 mg, 21 μmol) was added, and toluene (30 ml) was further added. A mixture of styrene (2.148 g, 21 mmol) and isoprene (1.431 g, 21 mmol) was added to the resulting solution, and a polymerization reaction was performed at 25 ° C. After 12 hours, methanol was added to terminate the polymerization reaction. The reaction mixture was poured into methanol (200 ml) to precipitate the polymer. The precipitated polymer was collected by filtration and dried at 60 ° C. under reduced pressure to obtain 1.64 g of isoprene-styrene copolymer.

<Examples 19 to 21> Production of isoprene-styrene copolymer In Example 18, except for changing the amounts of styrene and isoprene as shown in the following table, isoprene-styrene copolymer A polymer was obtained.

<Example 22> Production of ethylene polymer In a glove box, (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (10 mg, 21 µmol), [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (19 mg, 21 μmol) and toluene (50 ml) were added to a 250 ml two-necked flask at room temperature. The flask was removed from the glove box and connected to a Schlenk line. The temperature of the flask was maintained at 25 ° C. using a water bath.
While rapidly stirring the inside of the flask, ethylene gas (1 atm) was continuously supplied and bubbled, and the polymerization reaction was continued for 10 minutes. After completion of the reaction, the reaction mixture was poured into methanol (400 ml) to precipitate the polymer. The white powder polymer was collected by filtration and dried at 60 ° C. to obtain 4.39 g (constant weight) of polymer. The ¹³ C-NMR spectrum chart of this polymer is shown in FIG. (Measurement solvent was 1,2-dichlorobenzene-d ₄ and measurement temperature was 130 ° C.)

<Example 23-30> preparation of ethylene polymer (1) Example 23: Except that in Example 22, the complex and _{(C 5 Me 4 SiMe 3)} Gd (CH 2 SiMe 3) 2 (THF), An ethylene polymer was obtained in the same manner.
(2) Example 24: An ethylene polymer was obtained in the same manner as in Example 22, except that the complex was (C ₅ Me ₄ SiMe ₃ ) Y (CH ₂ SiMe ₃ ) ₂ (THF).
(3) Example 25: An ethylene polymer was obtained in the same manner as in Example 22 except that the complex was changed to (C ₅ Me ₄ SiMe ₃ ) Ho (CH ₂ SiMe ₃ ) ₂ (THF).
(4) Example 26: An ethylene polymer was obtained in the same manner as in Example 22, except that the complex was (C ₅ Me ₄ SiMe ₃ ) Lu (CH ₂ SiMe ₃ ) ₂ (THF).
(5) Example 27: An ethylene polymer was obtained in the same manner as in Example 22 except that the complex was (C ₅ Me ₄ SiMe ₃ ) Er (CH ₂ SiMe ₃ ) ₂ (THF).
(6) Example 28: An ethylene polymer was obtained in the same manner as in Example 22, except that the complex was (C ₅ Me ₄ SiMe ₃ ) Dy (CH ₂ SiMe ₃ ) ₂ (THF).
(7) Example 29: An ethylene polymer was obtained in the same manner as in Example 22, except that the complex was (C ₅ Me ₄ SiMe ₃ ) Tb (CH ₂ SiMe ₃ ) ₂ (THF).
(8) Example 30: An ethylene polymer was obtained in the same manner as in Example 22 except that the complex was (C ₅ Me ₄ SiMe ₃ ) Tm (CH ₂ SiMe ₃ ) ₂ (THF).

  The production methods of Examples 22 to 30 and the physical properties of the obtained ethylene polymers are shown in Table 4.

In Table 4, The activity is expressed as the number of kg of polymer produced by reacting for 1 hour at 1 atmosphere of ethylene using 1 mol of the complex.
2. The number average molecular weight and molecular weight distribution (Mw / Mn) were calculated by the GPC method (measured at 145 ° C. using polystyrene as a standard and 1,2-dichlorobenzene as an eluent).

  As shown in Table 4, it can be seen that the composition of the present invention containing a complex having a Group 3 metal or a lanthanoid metal as a central metal is used as a polymerization catalyst composition.

In <Example 31> during manufacturing glove box 1-hexene _{polymer, (C 5 Me 4 SiMe 3} ) Sc (CH 2 SiMe 3) 2 (THF) (10 mg, 21μmol) in toluene (5 ml) and of A toluene solution (8 ml) of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (19 mg, 21 μmol) was added to a 100 ml glass reaction vessel at room temperature.
Several minutes later, 1-hexene (1.736 g, 21 mmol) was added to the resulting wine red catalyst solution while stirring. The polymerization reaction was continued for 15 minutes. After completion of the reaction, methanol (70 ml) was added to precipitate an oily polymer. The obtained polymer was dried at 60 ° C. under reduced pressure to obtain 1.684 g (constant weight) of polymer (97%). The ¹³ C-NMR spectrum chart of this polymer is shown in FIG. (Measurement solvent was 1,2-dichlorobenzene-d ₄ and measurement temperature was 130 ° C.)

<Examples 32-35> Production of 1-hexene polymer (1) Example 32: In Example 31, the reaction temperature was changed to -30 ° C and the reaction time was changed to 60 minutes. -A hexene polymer was obtained.
(2) Example 33: A 1-hexene polymer was obtained in the same manner as in Example 31, except that the amount of 1-hexene was 2.604 g and the reaction time was 30 minutes.
(3) Example 34: The 1-hexene polymer was prepared in the same manner as in Example 31 except that the complex was changed to (C ₅ Me ₅ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (21 μmol). Obtained.
(4) Example 35: 1 in the same manner as in Example 31, except that the complex was changed to (C ₅ (SiMe ₃ ) ₂ H ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (21 μmol). -A hexene polymer was obtained.

In Table 5, The yield was calculated by (mass of polymer obtained) / (mass of monomer used).
2. The number average molecular weight and molecular weight distribution (Mw / Mn) were calculated by the GPC method (measured at 40 ° C. using polystyrene as a standard and THF as an eluent).

<Example 36> Production of 1-hexene-ethylene copolymer In a glove box, 1-hexene (1.736 g, 21 mmol) and toluene (15 ml) were mixed with 250 ml of glass with a stirring bar. Added to the neck flask. The reaction vessel was removed from the glove box and connected to a Schlenk line. The temperature of the reaction vessel was maintained at 25 ° C. using a water bath, and ethylene gas (1 atm) was supplied and bubbled while rapidly stirring the contents.
In toluene (15 ml), (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (10 mg, 21 μmol), and [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (19 mg, 21 μmol) was reacted to generate a predetermined amount of active species in the system. This was quickly added to the hexene-ethylenetoluene solution described above with a syringe to initiate the polymerization reaction. After 5 minutes, methanol was added to terminate the polymerization reaction, and the reaction mixture was poured into methanol (400 ml) to precipitate the polymer. The precipitated polymer was collected by filtration and dried at 60 ° C. under reduced pressure to obtain 1.92 g (constant weight) of polymer. The ¹³ C-NMR spectrum chart of this polymer is shown in FIG. (Measured at 120 ° C using 1,1,2,2-tetrachloroethane-d2 as the measurement solvent)

<Examples 37 to 49> Production of 1-hexene-ethylene copolymer (1) Example 37: In Example 36, a polymer was obtained in the same manner except that the amount of 1-hexene was changed to 10 mmol. It was.
(2) Example 38: A polymer was obtained in the same manner as in Example 36 except that the amount of 1-hexene was 31 mmol.
(3) Example 39: A polymer was obtained in the same manner as in Example 36 except that the amount of 1-hexene was changed to 41 mmol.
(4) Example 40: A polymer was obtained in the same manner as in Example 36 except that the amount of 1-hexene was changed to 62 mmol.
(5) Example 41 A polymer was obtained in the same manner as in Example 36 except that the reaction time was 3 minutes.
(6) Example 42: A polymer was obtained in the same manner as in Example 36 except that the reaction time was 7 minutes.
(8) Example 43: A polymer was obtained in the same manner as in Example 36 except that the reaction time was 10 minutes.
(9) Example 44: A polymer was obtained in the same manner as in Example 36 except that the reaction time was 15 minutes.
(10) Example 45: A polymer was obtained in the same manner as in Example 36 except that the complex was (C ₅ Me ₅ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF).
(11) Example 46: A polymer was obtained in the same manner as in Example 45 except that the amount of 1-hexene was 31 mmol and the reaction time was 3 minutes.
(12) Example 47: A polymer was obtained in the same manner as in Example 45 except that the amount of 1-hexene was 41 mmol and the reaction time was 3 minutes.
(13) Example 48: A polymer was obtained in the same manner as in Example 45 except that the amount of 1-hexene was 31 mmol.
(14) Example 49: A polymer was obtained in the same manner as in Example 45 except that the reaction time was 15 minutes.

  The production methods of Examples 36 to 49 and the physical properties of the obtained copolymers are summarized in Table 6.

In Table 6,
The 1.1-hexene content was calculated from a ¹ H-NMR spectrum (measured at 120 ° C. using 1,1,2,2-tetrachloroethane-d2 as a measurement solvent).
2. The number average molecular weight and molecular weight distribution (Mw / Mn) were measured by the GPC method (polystyrene as a standard substance, and 1,2-dichlorobenzene was used as an eluent).

Example 50 Production of Copolymer of Styrene and p-Methylstyrene In a glove box, (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (10 mg, 21 μmol) and [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (19 mg, 21 μmol) was added to toluene (30 ml) in a 100 ml reaction vessel, and styrene (4.076 g, 39 mmol) and 4- A mixture of methylstyrene (0.243 g, 2 mmol) was added, and a polymerization reaction was carried out at 25 ° C. After 5 minutes, methanol was added to terminate the polymerization reaction, and the reaction mixture was poured into methanol (200 ml) to precipitate the polymer. The precipitated polymer was collected by filtration and dried at 60 ° C. under reduced pressure to obtain 4.32 g (constant weight) of polymer.

<Examples 51-58> Production of Copolymer of Styrene and p-Methylstyrene (1) Example 51: In Example 50, the molar ratio of styrene to 4-methylstyrene was 90:10 (total The polymer was obtained in the same manner except that the molar amount was 41 mmol).
(2) Example 52: A polymer was obtained in the same manner as in Example 50 except that the molar ratio of styrene and 4-methylstyrene was changed to 70:30 (the total molar amount was 41 mmol).
(3) Example 53: A polymer was obtained in the same manner as in Example 50 except that the molar ratio of styrene to 4-methylstyrene was 50:50 (total molar amount was 41 mmol).
(4) Example 54: A polymer was obtained in the same manner as in Example 50 except that the molar ratio of styrene to 4-methylstyrene was 30:70 (total molar amount was 41 mmol).
(5) Example 55: A polymer was obtained in the same manner as in Example 50, except that the molar ratio of styrene to 4-methylstyrene was 5:95 (total molar amount was 41 mmol).
(6) Example 56: In Example 50, 4-methylstyrene is changed to 4-t-butylstyrene, and the molar ratio of styrene to 4-t-butylstyrene is 50:50 (total molar amount is 41 except that the polymer was obtained in the same manner.
(7) Example 57: A polymer was obtained in the same manner as in Example 56, except that the molar ratio of styrene and 4-t-butylstyrene was 70:30 (total molar amount was 41 mmol). It was.
(8) Example 58: A polymer was obtained in the same manner as in Example 56 except that the molar ratio of styrene to 4-t-butylstyrene was 30:70 (the total molar amount was 41 mmol). It was.

  The production methods of Examples 50 to 58 and the physical properties of the obtained copolymers are summarized in Table 7.

In Table 7,
1. The yield was calculated by “(mass of polymer obtained) / (mass of monomer used)”.
2. The styrene content was calculated from a ¹³ C-NMR spectrum and a ¹ H-NMR spectrum (measured at 130 ° C. using 1,2-dichlorobenzene as a measurement solvent).
3. The number average molecular weight and molecular weight distribution (Mw / Mn) were measured by the GPC method (polystyrene as a standard substance, and 1,2-dichlorobenzene was used as an eluent).
4). Syndiotacticity was determined from a ¹³ C-NMR spectrum.

<Example 59> Production of copolymer of ethylene and norbornene In a glove box, a toluene solution (15 ml) of norbornene (1.88 g, 20.0 mmol), [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] 2 ml of toluene solution (21 ml) of (19 mg, 21 μmol) and toluene (13 ml) were added to (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (10 mg , 21 μmol) of a toluene solution (21 ml) and a two-necked flask equipped with a dropping funnel containing toluene (8 ml) (total amount of toluene 40 ml).
The flask was removed from the glove box, set in a water bath (25 ° C.), and connected to a shrink tube, an ethylene gas supply tube, and a mercury shield stopper. While supplying ethylene gas, the solution in the dropping funnel was added. After completion of the dropwise addition, the reaction was allowed to proceed for 5 minutes, and methanol (25 ml) was added to stop the reaction.
The precipitated polymer was collected by filtration and washed with methanol. It was dried at 60 ° C. for 24 hours under reduced pressure. The obtained crude product was extracted with toluene at room temperature to obtain 0.67 g of an ethylene-norbornene alternating copolymer.

<Examples 60 to 74> Production of copolymer of ethylene and norbornene (1) Example 60: In Example 59, the complex was converted to {1,3- (SiMe ₃ ) ₂ C ₅ H ₃ } Sc (CH ₂ A polymer was obtained in the same manner except that SiMe ₃ ) ₂ (THF) was used.
(2) Example 61: A polymer was obtained in the same manner as in Example 59 except that the reaction temperature was 0 ° C.
(3) Example 62: A polymer was obtained in the same manner as in Example 59 except that the reaction temperature was 50 ° C.
(4) Example 63: A polymer was obtained in the same manner as in Example 59 except that the reaction temperature was 70 ° C.
(5) Example 64: A polymer was obtained in the same manner as in Example 59 except that the total amount of toluene was adjusted to 60 ml.
(6) Example 65: A polymer was obtained in the same manner as in Example 59 except that the total amount of toluene was adjusted to 20 ml.
(7) Example 66: A polymer was obtained in the same manner as in Example 59 except that the total amount of toluene was adjusted to 10 ml.
(8) Example 67: A polymer was obtained in the same manner as in Example 59 except that the amount of norbornene was changed to 2.82 g. The ¹³ C-NMR spectrum chart of this polymer is shown in FIG. (Measurement solvent was 1,2-dichlorobenzene-d ₄ and measurement temperature was 130 ° C.)
(9) Example 68: A polymer was obtained in the same manner as in Example 59 except that the amount of norbornene was changed to 3.76 g.
(10) Example 69: A polymer was obtained in the same manner as in Example 59 except that the reaction time was 1 minute.
(11) Example 70: A polymer was obtained in the same manner as in Example 59 except that the reaction time was 3 minutes.
(12) Example 71: A polymer was obtained in the same manner as in Example 59 except that the reaction time was 15 minutes.
(13) Example 72: A polymer was obtained in the same manner as in Example 59 except that the reaction time was 30 minutes.
(14) Example 73: A polymer was obtained in the same manner as in Example 59, except that the amount of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] was 0.
(15) Example 74: A polymer was obtained in the same manner as in Example 59 except that the amount of (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) used was changed to 0. .

The production methods of Examples 59 to 74 and the physical properties of the obtained polymers are summarized in Table 8. NB represents norbornene. In the column of the catalyst composition, 1 represents (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF), and 2 represents {1,3- (SiMe ₃ ) ₂ C ₅ H ₃ } Sc (CH ₂ Represents SiMe ₃ ) ₂ (THF).

In Table 8,
1. The activity is expressed as the number of kg of polymer produced by reacting for 1 hour using 1 mol of the complex.
2. Number average molecular weight and molecular weight distribution (Mw / Mn) were measured by GPC method (polystyrene was used as a standard substance).
3. The melting point was measured by DSC method.
The polymers obtained in Examples 59 to 72 were all ethylene-norbornene alternating copolymers.

<Example 75> Stereospecific polymerization reaction of 1,3-cyclohexadiene In a glove box, a toluene solution (3 ml) of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (37 mg, 40 μmol) Was added to a toluene solution (2 ml) of (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (19 mg, 40 μmol) in a 100 ml flask. The resulting mixture was stirred at room temperature for several minutes and then 1,3-cyclohexadiene (0.8 g, 10 mmol) was added with vigorous stirring. After 3 hours, the flask was removed from the glove box, and methanol was added to terminate the polymerization. The obtained reaction mixture was poured into methanol (200 ml), and the precipitated white polymer powder was collected by filtration. The powder collected by filtration was dried at 60 ° C. under reduced pressure to obtain 0.44 g of a polymer product (55%). The product obtained was dissolved in dichlorobenzene at 120 ° C.

<Examples 76 to 82> Stereospecific polymerization reaction of 1,3-cyclohexadiene (1) Example 76: In Example 75, [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (37 mg, Instead of [Ph (Me) ₂ NH] [B (C ₆ F ₅ ) ₄ ] (32 mg, 40 μmol) instead of 40 μmol), 0.16 g of polymer product was obtained (24 %). The product obtained was dissolved in dichlorobenzene at 120 ° C.
(2) Example 77: In Example 75, instead of (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (19 mg, 40 μmol), (C ₅ Me ₅ ) Sc (CH 0.34 g of polymer product was obtained (43%) in the same manner except that ₂ SiMe ₃ ) ₂ (THF) (17 mg, 40 μmol) was used. The product obtained was dissolved in dichlorobenzene at 120 ° C.
(3) Example 78: In Example 75, instead of (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (19 mg, 40 μmol), (C ₅ Me ₄ SiMe ₃ ) Y 0.30 g of polymer product was obtained in the same manner except that it was changed to (CH ₂ SiMe ₃ ) ₂ (THF) (21 mg, 40 μmol) (38%). The product obtained was dissolved in dichlorobenzene at 120 ° C.
(4) Example 79: In Example 75, instead of (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (19 mg, 40 μmol), (C ₅ Me ₄ SiMe ₃ ) Lu 0.29 g of polymer product was obtained in the same manner except that it was changed to (CH ₂ SiMe ₃ ) ₂ (THF) (25 mg, 40 μmol) (36%). The product obtained was dissolved in dichlorobenzene at 120 ° C.
(5) Example 80: In Example 75, instead of (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (19 mg, 40 μmol), (C ₅ Me ₄ SiMe ₃ ) Dy 0.39 g of polymer product was obtained (49%) in the same manner except that it was changed to (CH ₂ SiMe ₃ ) ₂ (THF) (24 mg, 40 μmol). The product obtained was dissolved in dichlorobenzene at 120 ° C.
(6) Example 81: In Example 75, instead of (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (19 mg, 40 μmol), (C ₅ Me ₄ SiMe ₃ ) Ho 0.40 g of polymer product was obtained in the same manner except that it was changed to (CH ₂ SiMe ₃ ) ₂ (THF) (19 mg, 40 μmol) (50%). The product obtained was dissolved in dichlorobenzene at 120 ° C.
(7) Example 82: In Example 75, instead of (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (19 mg, 40 μmol), (C ₅ Me ₄ SiMe ₃ ) Er 0.37 g of polymer product was obtained in the same manner except that it was changed to (CH ₂ SiMe ₃ ) ₂ (THF) (24 mg, 40 μmol) (46%). The product obtained was dissolved in dichlorobenzene at 120 ° C.

  Table 9 summarizes the physical properties of the polymer products obtained in Examples 75 to 82.

<Example 83> Copolymerization reaction of 1,3-cyclohexadiene and styrene In a glove box, a toluene solution (3 ml) of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (61 mg, 67 μmol) Was added to a toluene solution (2 ml) of (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (32 mg, 67 μmol) in a 100 ml flask. The resulting mixture was stirred for several minutes at room temperature, and then a toluene solution (5 ml) of 1,3-cyclohexadiene (1.26 g, 15.75 mmol) and styrene (0.55 g, 5.25 mmol) was added with vigorous stirring. After 3 hours, the flask was removed from the glove box, and methanol was added to terminate the polymerization. The obtained reaction mixture was poured into methanol (200 ml), and the precipitated white polymer powder was collected by filtration. The filtered powder was dried at 60 ° C. under reduced pressure to obtain 0.99 g of a polymer product (activity: 4.9 kg copolymer / mol Sc h). The resulting product was dissolved in THF.

<Examples 84 to 88> Copolymerization reaction of 1,3-cyclohexadiene and styrene (1) Example 84: In Example 83, the amount of 1,3-cyclohexadiene was changed from 1.26 g (15.75 mmol) to 1.12 g ( 14.00 mmol) and 1.13 g of polymer product was obtained in the same manner except that the amount of styrene was changed from 0.55 g (5.25 mmol) to 0.72 g (7.00 mmol) (activity: 5.6 kg copolymer / mol Sc h). The resulting product was dissolved in THF.
(2) Example 85: In Example 83, the amount of 1,3-cyclohexadiene was changed from 1.26 g (15.75 mmol) to 0.96 g (12.00 mmol), and the amount of styrene was changed from 0.55 g (5.25 mmol). 1.33 g of polymer product was obtained in the same manner except that the amount was changed to 0.94 g (9.00 mmol) (activity: 6.6 kg copolymer / mol Sc h). The resulting product was dissolved in THF.
(3) Example 86: In Example 83, the amount of 1,3-cyclohexadiene was changed from 1.26 g (15.75 mmol) to 0.84 g (10.50 mmol), and the amount of styrene was changed from 0.55 g (5.25 mmol). 1.46 g of polymer product was obtained in the same manner except that it was changed to 1.09 g (10.50 mmol) (activity: 7.3 kg copolymer / mol Sc h). The resulting product was dissolved in THF.
(4) Example 87: In Example 83, the amount of 1,3-cyclohexadiene was changed from 1.26 g (15.75 mmol) to 0.56 g (7.00 mmol), and the amount of styrene was changed from 0.55 g (5.25 mmol). 1.60 g of polymer product was obtained in the same manner except that it was changed to 1.46 g (14.00 mmol) (activity: 8.0 kg copolymer / mol Sc h). The resulting product was dissolved in THF.
(5) Example 88: In Example 83, the amount of 1,3-cyclohexadiene was changed from 1.26 g (15.75 mmol) to 0.42 g (5.25 mmol), and the amount of styrene was changed from 0.55 g (5.25 mmol). 2.00 g of polymer product was obtained in the same manner except that it was changed to 1.64 g (15.75 mmol) (activity: 10.0 kg copolymer / mol Sc h). The resulting product was dissolved in THF.

  Table 10 shows the physical properties of the polymer products obtained in Examples 83 to 88.

<Example 89> Copolymerization reaction of 1,3-cyclohexadiene and ethylene In a glove box, a toluene solution (15 ml) of 1,3-cyclohexadiene (0.4 g, 5.0 mmol) was mixed into a two-necked bar having a stirring bar. Placed in flask. The flask was removed from the glove box, set in a water bath (25 ° C.), and connected to a Schlenk ethylene line and a mercury-sealed stopper using a three-neck cock. Ethylene gas (1 atm) was fed into the system and stirred for 1 minute to saturate the solution.
On the other hand, from (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (19 mg, 40 μmol) and [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (37 mg, 40 μmol) A catalytic toluene solution (5 ml) was obtained. This catalyst toluene solution was added into the vigorously stirred solution of 1,3-cyclohexadiene using a syringe.
After 5 minutes, methanol (200 ml) was added to stop the polymerization reaction. The precipitated polymer product was collected by filtration. The product collected by filtration was washed with methanol and dried at 60 ° C. to obtain 1.31 g of a polymer product (activity: 3.9 × 105 g copolymer / mol Schatm). The product obtained was dissolved in 145 ° C. dichlorobenzene.

<Examples 90 to 96> Copolymerization reaction of 1,3-cyclohexadiene and ethylene (1) Example 90: In Example 89, the amount of 1,3-cyclohexadiene was changed from 0.4 g (5.0 mmol) to 0.5 g. 0.87 g of polymer product was obtained in the same manner except that it was changed to (6.3 mmol). The product obtained was dissolved in 145 ° C. dichlorobenzene.
(2) Example 91: In Example 89, except that the amount of 1,3-cyclohexadiene was changed from 0.4 g (5.0 mmol) to 0.6 g (7.5 mmol), 0.35 g of polymer was produced. I got a thing. The product obtained was dissolved in 145 ° C. dichlorobenzene.
(3) Example 92: 0.29 g of polymer was produced in the same manner as in Example 89 except that the amount of 1,3-cyclohexadiene was changed from 0.4 g (5.0 mmol) to 0.8 g (10.0 mmol). I got a thing. The product obtained was dissolved in 145 ° C. dichlorobenzene.
(4) Example 93: In the same manner as in Example 89, except that the temperature of the water bath was changed from 25 ° C. to 50 ° C., 2.00 g of a polymer product was obtained. The product obtained was dissolved in 145 ° C. dichlorobenzene.
(5) Example 94: 0.15 g of polymer was produced in the same manner as in Example 89 except that the amount of 1,3-cyclohexadiene was changed from 0.4 g (5.0 mmol) to 1.0 g (12.5 mmol). I got a thing. The product obtained was dissolved in 145 ° C. dichlorobenzene.
(6) Example 95: 0.08 g of polymer was produced in the same manner as in Example 89, except that the amount of 1,3-cyclohexadiene was changed from 0.4 g (5.0 mmol) to 1.2 g (15.0 mmol). I got a thing. The product obtained was dissolved in 145 ° C. dichlorobenzene.
(7) Example 96: In Example 89, the amount of 1,3-cyclohexadiene was changed from 0.4 g (5.0 mmol) to 2.0 g (25.0 mmol), and the temperature of the water bath was changed from 25 ° C. to 50 ° C. In the same manner, 0.20 g of a polymer product was obtained. The product obtained was dissolved in 145 ° C. dichlorobenzene.

  Table 11 shows the physical properties of the polymer compositions obtained in Examples 89 to 96.

<Example 97> Ternary copolymerization reaction of ethylene, styrene, and norbornene In a glove box, a toluene solution (35 ml) of 2-norbornene (1.88 g, 20 mmol) and styrene (0.52 g, 5 mmol) was stirred. Placed in a two-neck flask with a bar. The flask was removed from the glove box, set in a water bath (25 ° C.), and connected to a Schlenk ethylene tube and a mercury shield stopper using a three-neck cock. Ethylene gas (1 atm) was fed into the system and stirred for 1 minute to saturate the solution.
On the other hand, from (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (10 mg, 21 μmol) and [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (19 mg, 21 μmol) A catalytic toluene solution (5 ml) was obtained. The obtained catalyst solution was added to the norbornene-styrene solution which was vigorously stirred with a syringe. The viscosity of the reaction mixture increased rapidly.
After 5 minutes, methanol (200 ml) was added to stop the polymerization reaction. The precipitated polymer product was collected by filtration, washed with methanol and dried at 60 ° C. to obtain 2.93 g of polymer product (activity: 1.7 × 10 ⁶ g terpolymer / mol Schatm). The resulting product was dissolved in 145 ° C. dichlorobenzene.

<Examples 98-101> Ethylene / styrene / norbornene terpolymerization reaction (1) Example 98: In Example 97, the amount of styrene was changed from 0.52 g (5 mmol) to 1.04 g (10 mmol). In the same manner, 2.69 g of polymer product was obtained in the same manner (activity: 1.5 × 10 ⁶ g terpolymer / mol Schatm). The resulting product was dissolved in 145 ° C. dichlorobenzene.
(2) Example 99: 3.00 g of polymer product was obtained in the same manner as in Example 97 except that the amount of styrene was changed from 0.52 g (5 mmol) to 2.08 g (20 mmol) (activity) : 1.7 x 10 ⁶ g terpolymer / mol Sc h atm). The resulting product was dissolved in 145 ° C. dichlorobenzene.
(3) Example 100: 3.45 g of a polymer product was obtained in the same manner as in Example 97 except that the amount of styrene was changed from 0.52 g (5 mmol) to 3.12 g (30 mmol) (activity) : 2.0 x 10 ⁶ g terpolymer / mol Sc h atm). The resulting product was dissolved in 145 ° C. dichlorobenzene.
(4) Example 101: 1.16 g of polymer product was obtained in the same manner as in Example 97 except that the amount of styrene was changed from 0.52 g (5 mmol) to 4.16 g (40 mmol) (activity) : 0.7 x 10 ⁶ g terpolymer / mol Sc h atm). The resulting product was dissolved in 145 ° C. dichlorobenzene.

  Table 12 shows the physical properties of the polymer compositions obtained in Examples 97 to 101.

<Example 102> Copolymerization reaction of dicyclopentadiene and ethylene In a glove box, a toluene solution (35 ml) of dicyclopentadiene (2.64 g, 20 mmol) was placed in a two-necked flask. The flask was removed from the glove box, set in a water bath (25 ° C.), and connected to a shrink ethylene tube and a mercury shield stopper using a three-necked flask. Ethylene gas (1 atm) was fed into the system and stirred for 1 minute to saturate the solution.
On the other hand, from (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (THF) (10 mg, 21 μmol) and [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ] (19 mg, 21 μmol) A catalytic toluene solution (5 ml) was prepared. The prepared catalyst solution was added to the vigorously stirred solution of dicyclopentadiene and ethylene with a syringe. The viscosity of the reaction mixture increased rapidly.
After 5 minutes, methanol (200 ml) was added to terminate the polymerization. The precipitated polymer product was collected by filtration, washed with methanol, and dried at 60 ° C. to give 2.3 g of polymer product (1.3 × 10 ⁶ g copolymer / mol Schatm). The product obtained was dissolved in 145 ° C. dichlorobenzene.

<Examples 103 to 104> Copolymerization reaction of dicyclopentadiene and ethylene (1) Example 103: In Example 102, the amount of dicyclopentadiene was changed from 2.64 g (20 mmol) to 3.96 g (30 mmol). Otherwise, 3.2 g of polymer product was obtained in the same manner (1.8 × 10 ⁶ g copolymer / mol Schatm). The product obtained was dissolved in 145 ° C. dichlorobenzene.
(2) Example 104: In Example 102, 4.0 g of a polymer product was obtained by the same method except that the amount of dicyclopentadiene was changed from 2.64 g (20 mmol) to 5.28 g (40 mmol). (2.3 x 10 ⁶ g copolymer / mol Sc h atm). The product obtained was dissolved in 145 ° C. dichlorobenzene.

  Table 13 shows the physical properties of the polymer products obtained in Examples 102 to 104.

  By using the polymerization catalyst composition of the present invention, new methods for producing various polymer compounds are provided, and new polymer compounds are further provided.

Claims (57)

1) Scandium Sc, gadolinium Gd, yttrium Y, holmium Ho, lutetium Lu, erbium Er, dysprosium Dy, terbium Tb or thulium Tm, central metal M, substituted or unsubstituted cyclopentadienyl derivative bonded to the central metal A metallocene complex represented by the general formula (I), which contains a ligand Cp ^* , monoanionic ligands Q ¹ and Q ² , and W neutral Lewis bases L, and 2) non-coordinating properties A polymerization catalyst composition comprising an ionic compound comprising an anion and a cation.

  The catalyst composition according to claim 1, wherein the central metal M in the metallocene complex is scandium Sc. The catalyst composition according to claim 1 or 2, wherein the ligand Cp ^* containing the cyclopentadienyl derivative is a non-bridged ligand. The cyclopentadienyl derivative contained in the ligand Cp ^* in the metallocene complex is tetramethyl (trimethylsilyl) cyclopentadienyl or pentamethylcyclopentadienyl. A catalyst composition according to claim 1. At least one of monoanionic ligands Q ¹ and Q ² in the metallocene complex is ortho - characterized in that it is a dimethylamino benzyl or trimethylsilylmethyl group, to any one of claims 1-4 The catalyst composition as described.   The catalyst composition according to any one of claims 1 to 5, wherein the neutral Lewis base L in the metallocene complex is tetrahydrofuran.   The catalyst composition according to any one of claims 1 to 6, which is a catalyst composition for polymerization of an olefin monomer.   The catalyst composition according to claim 7, wherein the olefin monomer is selected from the group consisting of unsubstituted styrene, substituted styrene, ethylene, α-olefin, diene, and norbornenes.   The catalyst composition according to any one of claims 1 to 6, which is a catalyst composition for copolymerization of two or more olefin monomers.   The two or more olefin monomers are two or more olefin monomers selected from the group consisting of unsubstituted styrene, substituted styrene, ethylene, α-olefin, diene, and norbornenes. The catalyst composition.   The catalyst composition according to claim 10, which is used for producing a copolymer of ethylene and substituted or unsubstituted styrene.   The catalyst composition according to claim 10, which is used for producing a copolymer of 1,3-cyclohexadiene and substituted or unsubstituted styrene.   The catalyst composition according to claim 10, which is used for producing a copolymer of 1,3-cyclohexadiene and ethylene.   The catalyst composition according to claim 10, which is used for producing a copolymer of ethylene, norbornene, and substituted or unsubstituted styrene.   The catalyst composition according to claim 10, which is used for producing a copolymer of dicyclopentadiene and ethylene.   A high or high syndicate of substituted or unsubstituted styrene, characterized in that Mw / Mn, which is an index of molecular weight distribution obtained by the catalyst composition according to any one of claims 1 to 6, is 1.7 or less. Tactic polymer.   The polymer according to claim 16, wherein the syndiotacticity is 80 rrrr% or more in pentad display.   Mw / Mn, which is an index of molecular weight distribution obtained by the catalyst composition according to any one of claims 1 to 6, is 1.7 or less, substituted or unsubstituted styrene and substituted styrene High syndiotactic copolymer.   The copolymer according to claim 18, wherein the syndiotacticity is 80 rrrr% or more in pentad display.   A high syndiotactic copolymer of ethylene and substituted or unsubstituted styrene obtained by the catalyst composition according to any one of claims 1 to 6.   21. The copolymer according to claim 20, which is a random copolymer and has a syndiotacticity of a chain composed of styrene structural units of 98 r% or more in terms of dyads.   21. The copolymer according to claim 20, which is a block copolymer, wherein the syndiotacticity of the styrene block chain is 80 rrrr% or more in pentad display.   The copolymer according to any one of claims 20 to 22, wherein Mw / Mn, which is an index of molecular weight distribution, is 1.3 or less.   The ratio of the styrene structural unit with respect to all the structural units is 5-99 mol%, The copolymer as described in any one of Claims 20-23 characterized by the above-mentioned.   A 1,3-cyclohexadiene polymer obtained by the catalyst composition according to any one of claims 1 to 6, wherein a ratio of 1,4-structural units to all structural units is 90% or more. And a high cis-syndiotactic polymer.   The polymer according to claim 25, wherein the cis-syndiotacticity is 70 rrrr% or more.   A copolymer of 1,3-cyclohexadiene and substituted or unsubstituted styrene obtained by the catalyst composition according to any one of claims 1 to 6, comprising all structural units of 1,3-cyclohexadiene A copolymer having a ratio of 1,4-structural units to 90% or more.   28. The copolymer according to claim 27, wherein the copolymer is a random copolymer and has a syndiotacticity of styrene structural units of 98 r% or more in terms of dyads.   A copolymer of 1,3-cyclohexadiene and ethylene obtained by the catalyst composition according to any one of claims 1 to 6.   30. The copolymer according to claim 29, wherein the ratio of 1,4-structural units to the total structural units of 1,3-cyclohexadiene is 90% or more.   A copolymer of ethylene, norbornenes, and substituted or unsubstituted styrene obtained by the catalyst composition according to any one of claims 1 to 6.   32. The copolymer according to claim 31, wherein the copolymer is a random copolymer and has a syndiotacticity of styrene structural units of 98 r% or more in terms of dyads.   A copolymer of dicyclopentadiene and ethylene obtained by the catalyst composition according to any one of claims 1 to 6, wherein the number average molecular weight is 100,000 or more. .   The copolymer according to claim 33, wherein the ratio of dicyclopentadiene structural units to all structural units is 10 mol% or more.   It is a manufacturing method of an olefin polymer, Comprising: An olefin monomer is polymerized using the polymerization catalyst composition as described in any one of Claims 1-6.   36. The process according to claim 35, wherein the olefin monomer is selected from the group consisting of substituted and unsubstituted styrene, ethylene, dienes, norbornenes and [alpha] -olefins.   It is a manufacturing method of an olefin copolymer, Comprising: Two or more olefin monomers are polymerized using the polymerization catalyst composition as described in any one of Claims 1-6.   38. The two or more olefin monomers are two or more olefin monomers selected from the group consisting of substituted and unsubstituted styrene, ethylene, diene, norbornenes, and [alpha] -olefins. Manufacturing method. The olefin polymer is a substituted or unsubstituted styrene polymer,
The production method according to claim 35, wherein the olefin monomer is substituted or unsubstituted styrene.   40. The production method according to claim 39, wherein the substituted or unsubstituted styrene polymer is a high syndiotactic polymer.   40. The production method according to claim 39, wherein the substituted or unsubstituted styrene polymer is the styrene polymer according to claim 16 or 17. The olefin copolymer is a styrene copolymer,
The method according to claim 37, wherein the olefin monomer is two or more styrenes selected from substituted and unsubstituted styrene.   43. The method according to claim 42, wherein the styrene copolymer is a high syndiotactic copolymer.   The method according to claim 42, wherein the styrene copolymer is the styrene copolymer according to claim 18 or 19. The olefin copolymer is a copolymer of ethylene and a substituted or unsubstituted styrene,
The production method according to claim 37, wherein the olefin monomer is ethylene and substituted or unsubstituted styrene.   The copolymer of ethylene and substituted or unsubstituted styrene is the copolymer of ethylene and substituted or unsubstituted styrene according to any one of claims 20 to 24. The method described. The olefin polymer is a 1,3-cyclohexadiene polymer,
36. The method according to claim 35, wherein the olefin monomer is 1,3-cyclohexadiene.   The manufacturing method according to claim 47, wherein the 1,3-cyclohexadiene polymer is the 1,3-cyclohexadiene polymer according to claim 25 or 26. The olefin copolymer is a copolymer of 1,3-cyclohexadiene and a substituted or unsubstituted styrene,
The method according to claim 37, wherein the olefin monomer is 1,3-cyclohexadiene and substituted or unsubstituted styrene.   50. The production method according to claim 49, wherein the copolymer of 1,3-cyclohexadiene and substituted or unsubstituted styrene is the copolymer according to claim 27 or 28. The olefin copolymer is a copolymer of 1,3-cyclohexadiene and ethylene,
The production method according to claim 37, wherein the olefin monomer is 1,3-cyclohexadiene and ethylene.   52. The production method according to claim 51, wherein the copolymer of 1,3-cyclohexadiene and ethylene is the copolymer according to claim 29 or 30. The olefin copolymer is a copolymer of ethylene, norbornenes, and substituted or unsubstituted styrene,
The production method according to claim 37, wherein the olefin monomer is ethylene, norbornene, and substituted or unsubstituted styrene. The manufacturing method according to claim 53 , wherein the copolymer is the copolymer according to claim 31 or 32. The olefin copolymer is a copolymer of dicyclopentadiene and ethylene,
The production method according to claim 37, wherein the olefin monomer is dicyclopentadiene and ethylene. The manufacturing method according to claim 55 , wherein the copolymer of dicyclopentadiene and ethylene is the copolymer according to claim 33 or 34. The olefin copolymer is a copolymer of substituted or unsubstituted styrene and a conjugated diene,
The production method according to claim 37, wherein the olefin monomer is substituted or unsubstituted styrene and a conjugated diene.

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